TWI493015B - Light-emitting organometallic complexes - Google Patents

Description

Luminescent organometallic complex

The present invention relates to an organic light-emitting device (OLED). More particularly, the present invention relates to luminescent organometallic materials and devices that can have improved device fabrication, fabrication, stability, efficiency, and/or color.

Optoelectronic devices using organic materials are becoming more and more desirable for a variety of reasons. Many of the materials used to make such devices are relatively inexpensive, and thus organic optoelectronic devices have the potential to cost advantage over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, make them extremely suitable for use in specific applications, such as fabrication on flexible substrates. Examples of the organic optoelectronic device include an organic light emitting device (OLED), an organic photoelectric transistor, an organic photovoltaic cell, and an organic photodetector. For OLEDs, organic materials can have performance advantages over conventional materials. For example, the wavelength of light emitted by the organic emissive layer can generally be easily adjusted with appropriate dopants.

OLEDs use a thin organic film that illuminates when a voltage is applied across the device. The use of OLEDs in applications such as flat panel displays, lighting and backlighting is becoming an increasingly interesting technology. A number of OLED materials and constructions are described in U.S. Patent Nos. 5,844,363, 6, 303, 238, and 5, 707, 745, the entireties of each of

One application of phosphorescent emitting molecules is a full color display. The industry standard for this display requires that it be suitable for emitting pixels of a particular color (called a "saturated" color). In particular, these standards require saturated red, green, and blue pixels. Color can be measured using CIE coordinates, which is well known in the art.

An example of a green emitting molecule is ruthenium (2-phenylpyridine) ruthenium (labeled Ir(ppy) ₃ ), which has the structure of formula I below:

Here and in the subsequent figures herein, the coordination bonds from nitrogen to metal (her Ir) are depicted as straight lines.

The term "organic" as used herein includes polymeric materials and small molecular organic materials that can be used in the fabrication of organic optoelectronic devices. "Small molecule" means any organic material that is not a polymer, and "small molecules" can actually be quite large. In some cases, small molecules can include repeating units. For example, the use of long chain alkyl groups as substituents does not exclude molecules from the "small molecule" category. Small molecules can also be incorporated into the polymer, for example as pendant groups on the polymer backbone or as part of the backbone. Small molecules can also be used as a core part of the dendrimer, which is composed of a series of chemical shells built on the core. The core portion of the dendrimer can be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be "small molecules" and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

As used herein, "top" means the farthest from the substrate, and "bottom" means the closest to the substrate. When the first layer is illustrated as being "disposed on" the second layer, then the first layer is disposed away from the substrate. Unless the first layer is indicated to be "in contact" with the second layer, there may be other layers between the first and second layers. For example, a cathode can be described as being "disposed on" an anode even with various organic layers in between.

As used herein, "solution treatable" means capable of dissolving, dispersing or transporting in a liquid medium and/or depositing from a liquid medium in the form of a solution or suspension.

When it is believed that the ligand contributes to the photoactive nature of the emissive material, it is said to have "photoactivity".

A more detailed description of the OLEDs, and the above definitions, can be found in U.S. Patent No. 7,279,704, the disclosure of which is incorporated herein in its entirety.

The present invention provides materials for use in OLEDs. These materials are 2-phenylpyridinium (Irppy) complexes having a ligand substituted with an alkyl group and/or an aryl group and a hetero- or homo-functional nature. These materials can be advantageously used in OLEDs.

These materials contain a heterocyclic compound having the formula:

Wherein n = 1 or 2; R ₁ , R ₂ , R ₃ , R ₄ and R _{5 are} independently selected from the group consisting of hydrogen, alkyl and aryl, and wherein R ₁ , R ₂ , R ₃ , R ₄ and R Each of ₅ may represent a mono-, di-, tri-, tetra- or penta-substituted group; and at least one of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ is an alkyl group or an aryl group.

In one aspect, the materials contain a heterocyclic compound having the formula:

Wherein n = 1 or 2; R ₁ , R ₂ , R ₅ and R _{6 are} independently selected from the group consisting of hydrogen, alkyl and aryl; at least one of R ₁ , R ₂ , R ₅ and R ₆ is alkyl or Aryl; and R ₃ , R ₄ and R _{7 are} independently selected from the group consisting of hydrogen, alkyl and aryl, and wherein R ₃ , R ₄ and R ₇ may represent mono-, di-, tri-, tetra- or penta-substituted.

In another aspect, the materials comprise a heteroquinone compound having the formula:

Wherein n = 1 or 2; R ₁ , R ₂ , R ₅ and R _{6 are} independently selected from the group consisting of hydrogen, alkyl and aryl; at least one of R ₁ , R ₂ , R ₅ and R ₆ is alkyl or An aryl group; and R ₃ , R ₄ and R _{7 are} independently selected from the group consisting of hydrogen, alkyl and aryl, and wherein each of R ₃ , R ₄ and R ₇ may represent a single, two, three, four or Five substitutions.

In another aspect, the materials comprise a heteroquinone compound having the formula:

Wherein n = 1 or 2; R ₁ and R _{4 are} independently selected from the group consisting of hydrogen, alkyl and aryl; at least one of R ₁ and R ₄ is alkyl or aryl; and R ₂ , R ₃ and R ₅ Independently selected from the group consisting of hydrogen, alkyl and aryl, and wherein each of R ₂ , R ₃ and R ₅ may represent a mono-, di-, tri-, tetra- or penta-substitution.

In another aspect, the materials comprise a heteroquinone compound having the formula:

Wherein n = 1 or 2; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R _{6 are} independently selected from the group consisting of hydrogen, alkyl and aryl, and wherein R ₁ , R ₂ , R ₃ , R ₄ , each of R ₅ and R ₆ may represent a mono-, di-, tri-, tetra- or penta-substituted; at least one of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ is an alkyl or aryl group; R _{1 is} different from R ₄ , R _{2 is} different from R ₅ , or R _{3 is} different from R ₆ .

In another aspect, the materials have a homologous compound selected from the group consisting of:

In another aspect, the materials have a coordination comprising a group selected from the group consisting of a compound of the formula wherein the ligand is coordinated to a metal having an atomic number greater than 40.

Further, the present invention provides an organic light-emitting device. The device comprises an anode, a cathode, and an organic emission layer disposed between the anode and the cathode, the organic layer further comprising an emission dopant, wherein the compound is the emission dopant. The organic emission layer further includes a host material. The present invention provides specific devices comprising a particular host material and specific dopants.

The present invention provides a process for the preparation of an Ir(L _a )(L _b )(L _c ) complex in an improved yield comprising the intermediate of formula (L _a )(L _b )IrX with L _c the reaction to produce _{Ir (L a) (L b} ) (L c) complexes, wherein L _a, L _b and L _c are independently-based photoactive and a bidentate ligand of the metal ring, having the formula: Wherein R ₃ , R ₄ , R ₅ , R ₆ , R′ ₃ , R′ ₄ , R′ ₅ and R′ _{6 are} independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl a group, CN, CO ₂ R, C(O)R, NR ₂ , NO ₂ , OR, halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl or heterocyclic group; wherein R At least one of ₆ or R' ₃ is not hydrogen, and R ₆ or R' ₃ is selected from the group consisting of alkyl, alkenyl, alkynyl, alkylaryl, CN, CO ₂ R, C(O R, NR ₂ , NO ₂ , OR, halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, and heterocyclic;

Typically, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects a hole into the organic layer, and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When the electrons and holes are on the same molecule, an "exciter" is formed, that is, a localized electron-hole pair having an excited energy state. When the exciter relaxes via a photoelectron emission mechanism, light can be emitted. In some cases, the excitons can be located on an excimer or exciplex. Non-radiative mechanisms (such as thermal relaxation) may also be present, but they are generally considered to be undesirable.

The initial OLED uses an emissive molecule that can emit light from its singlet state ("fluorescent"), as disclosed, for example, in U.S. Patent No. 4,769,292, the disclosure of which is incorporated herein in its entirety by reference. Fluorescence emission typically occurs within a time frame of less than 10 nanoseconds.

Recently, OLEDs having an emissive material that emits light from a triplet state ("phosphorescence") have been demonstrated. Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices", Nature, Vol. 395, 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light-emitting devices" Based on electrophosphorescence", Appl. Phys. Lett, Vol. 75, No. 1, 4-6 (1999) ("Baldo-II"), the entire disclosure of which is incorporated herein by reference. Phosphorescence is described in more detail in the US Patent 7,279,704, lines 5-6, which are incorporated by reference.

Phosphorescence emitted from a triplet state can enhance over-fluorescence by limiting organic molecules to (preferably via bonding) in close proximity to high atomic number atoms. This phenomenon, known as the heavy atom effect, is produced by a mechanism known as spin-orbit coupling. This phosphorescence transition can be observed from an excited metal to ligand charge transfer (MLCT) state of an organometallic molecule (eg, ruthenium (2-phenylpyridine) ruthenium (III)).

FIG. 1 shows an organic light emitting device 100. The figures are not necessarily to scale. The device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emission layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, and a protective layer 155. And a cathode 160. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by depositing the layers in sequence. The nature and function of the various layers and example materials are described in more detail in U.S. Patent No. 7,279,704, lines 6-10, which is incorporated herein by reference.

More examples of each of these layers can be utilized. For example, the flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, the disclosure of which is incorporated herein in its entirety by reference. An example of a p-doped hole transport layer is m-MTDATA doped with a 50:1 molar ratio by F.sub.4-TCNQ, as disclosed in U.S. Patent Application Publication No. 2003/0230980 The full text of the case is hereby incorporated by reference. An example of a launching and a host material is disclosed in U.S. Patent No. 6,303,238, the disclosure of which is incorporated herein by reference. An example of an n-doped electron transport layer is doped with Li at a molar ratio of 1:1. The entire disclosure of which is incorporated herein by reference in its entirety by reference. U.S. Pat. Nos. Composite cathode of ITO layer. The theory and use of the barrier layer is described in more detail in U.S. Patent No. 6,097,147, and U.S. Patent Application Serial No. 2003/0230, the entire disclosure of which is incorporated herein by reference. An example of an injection layer is provided in U.S. Patent Application Publication No. 2004/0174116, the entire disclosure of which is incorporated herein by reference. A description of the protective layer can be found in U.S. Patent Application Publication No. 2004/0174116, the entire disclosure of which is incorporated herein by reference.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 can be fabricated by depositing the layers in sequence. Since the most common OLED construction has a cathode disposed on the anode and the device 200 has a cathode 215 disposed under the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those set forth for device 100 can be used for corresponding layers of device 200. Figure 2 provides an example of how to omit some layers from the structure of device 100.

The simple layered structure shown in Figures 1 and 2 is provided in a non-limiting example form, and it should be understood that embodiments of the invention may be utilized in connection with various other structures. The particular materials and structures are illustrative in nature and other materials and structures can be used. Functional OLEDs can be achieved by combining the various layers in different ways, or multiple layers can be completely based on design, performance and cost factors Omitted. Other layers not specifically described may also be included. Materials other than those specifically recited materials may be used. While many of the examples provided herein illustrate that the various layers comprise a single material, it will be appreciated that a combination of materials (e.g., a mixture of host material and dopant) can be used or a mixture can generally be used. Moreover, the layers can have various sub-layers. The names provided herein for the various layers are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be illustrated as a hole transport layer or a hole injection layer. In one embodiment, an OLED can be illustrated as having an "organic layer" disposed between a cathode and an anode. The organic layer may comprise a single layer or may further comprise, for example, multiple layers of different organic materials as described with reference to Figures 1 and 2.

</ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; in. By way of further example, an OLED having a single organic layer can be used. The OLEDs can be stacked, for example, as described in U.S. Patent No. 5,707,745, the entire disclosure of which is incorporated herein by reference. The OLED structure can deviate from the simple layered structure shown in Figures 1 and 2. For example, the substrate can include an angled reflective surface to improve the output coupling, such as the mesa structure described in U.S. Patent No. 6,091,195 to the name of U.S. Patent No. 6,091,195, issued to U.S. Pat. The pit structures described in the above are incorporated herein by reference in their entirety.

Unless otherwise stated, any layer of each embodiment may be adapted by any means. The method should be deposited. The preferred method for the organic layer includes thermal evaporation, ink jet (for example, as described in U.S. Patent Nos. 6,013,982 and 6,087,196, the entire contents of each of each of Deposition (OVPD) (for example, as described in U.S. Patent No. 6,337,102 to the entire disclosure of which is incorporated herein in U.S. Patent Application Serial No. 10/233,470, the entire disclosure of which is incorporated herein by reference. Other suitable deposition methods include spin coating and other solution based methods. The solution based process is preferably carried out under nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation. The preferred method of patterning includes deposition by means of a mask, and cold soldering (for example, as described in U.S. Patent Nos. 6,294,398 and 6,468,819, the entireties of each of each of Inkjet and OVJD) related patterning methods. Other methods can also be used. The material to be deposited can be modified to suit a particular deposition method. For example, substituents such as alkyl or aryl groups having a branched or unbranched group and preferably containing at least 3 carbon atoms may be used in the small molecule to enhance their ability to carry out solution treatment. Substituents having 20 carbons or more may be used, and 3-20 carbons are preferred ranges. Materials with asymmetric structures may have better solution handling capabilities than materials with symmetric structures, as asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents can be used to enhance the ability of small molecules to undergo solution processing.

Devices made in accordance with embodiments of the present invention can be incorporated into a variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, and Or external lighting and / or signal lights, heads up display, fully transparent display, flexible display, laser printing machine, telephone, mobile phone, personal digital assistant (PDA), laptop, digital camera, camcorder, field of view Viewfinder, microdisplay, vehicle, large wall, theater or large stadium display or signboard. Various control mechanisms can be used to control the device made in accordance with the present invention, including a passive matrix and an active matrix. Many devices are intended to be used in a temperature range that is comfortable for people, such as 18 degrees Celsius to 30 degrees Celsius, and more preferably at room temperature (20-25 degrees Celsius).

The materials and structures described herein can be used in devices other than OLEDs. For example, other optoelectronic devices, such as organic solar cells and organic photodetectors, can use such materials and structures. More generally, organic materials such as organic transistors can use such materials and structures.

The terms halo, halo, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic, aryl, aromatic and heteroaryl are customary and defined by the art. In U.S. Patent No. 7,279,704, lines 31-32, which is incorporated herein by reference.

The present invention provides compounds comprising a ruthenium Ir(III) complex having a photoactive, space-requiring cyclometallated ligand. An advantage of using a ligand having a substituent such as an alkyl group and an aryl group is that it can provide illumination and device property adjustment while having only a small effect on device operational stability. In particular, the incorporation of an aryl group and an alkyl substituted ligand into a ruthenium complex can be used to achieve a device having high efficiency and high stability. See Kwong et al., Complexes with phenylpyridine derivatives and their use in organic light-emitting devices , 2006, WO 2006/014599 and Kwong et al. Stable and efficient electroluminescent materials , 2006, WO 2006/014599 A2.

Many cyclometallated ligands that can incorporate Ir-based phosphors do not achieve the rhodium-ligand complex by the synthetic methods reported. In many cases, an anthracene complex complex is significantly superior to a phosphorescent material as a complex having two cyclometallated ligands and a single bidentate or two monodentate ancillary ligands. Without wishing to be bound by theory, it is believed that the bond between Ir and the cyclometallated ligand is relatively stable, which means that it will not be easily replaced, thereby improving luminous efficiency. See Lamansky et al., Synthesis and Characterization of Phosphorescent Cyclometallated Iridium Complexes , Inorg. Chem., 40: 1704-1711, 2001 and Kwong et al., Organic Light Emitting Devices Having Reduced Pixel Shrinkage , col. 16, ln. 45-60, 2006, U.S. Patent No. 7,087,321 B2. Accordingly, it would be highly desirable to provide a process for preparing an Ir(III) complex having a photoactive ligand selected for use in an OLED in improved yield. This synthesis is particularly difficult for the emission of Ir(III) complexes of the formula: Wherein R ₃ , R ₄ , R ₅ , R ₆ , R ' ₃ , R ' ₄ , R ' ₅ and R' _{6 are} independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl a group, CN, CO ₂ R, C(O)R, NR ₂ , NO ₂ , OR, halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, and heterocyclic group; At least one of R ₆ and R′ ₃ is not hydrogen, and R ₆ and R′ ₃ are selected from the group consisting of alkyl, alkenyl, alkynyl, alkylaryl, CN, CO ₂ R, C ( O) R, NR ₂ , NO ₂ , OR, halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl and heterocyclic groups. Since the plurality of R ₆ and/or R' ₃ near Ir in the final anthracycline metalized Ir complex converges the space, the direct mismatch of the cyclometallated ligand with Ir(acac) ₃ may result in a desired The yield of the product is extremely low (about 10%). See Kwong et al., Complexes with phenylpyridine derivatives and their use in organic light-emitting devices , 2006, WO 2006/014599. The current approach is illustrated below: This reaction is reported to have a 5.4% yield.

The complexes provided with alkyl and/or aryl substitutions can have homogenous or heteromeric properties that can be used in PHOLED devices to achieve stable and efficient devices with more saturated colors. These materials can advantageously be used as emission dopants in PHOLED devices. Heterotypic complexes may be advantageous in some cases due to the different ligands imparting the desired properties. For example, assuming containing Ir (L _{1) 3} of the first device comprising emitter Ir (L _{2) 3} rather emitter of the second device, wherein the first device is more stable and means for transmitting two similar colors . However, if L ₁ has a higher molecular weight than L ₂ , Ir(L ₁ ) ₃ will require a higher vacuum evaporation temperature than Ir(L ₂ ) ₃ , thereby reducing the attractive force of using Ir(L ₁ ) ₃ . In this case, the hetero-isolated Ir(L ₁ )(L ₂ ) ₂ or Ir(L ₁ ) ₂ (L ₂ ) complex may have desirable characteristics imparted by the respective ligands (ie, L _{1 is} imparted well) Stability, while L ₂ gives a reduced molecular weight and a lower evaporation temperature). Moreover, in another case, if Ir(L ₁ ) _{3 is} insoluble and Ir(L ₂ ) _{3 is} soluble in most organic solvents, Ir(L ₁ ) ₃ cannot be used in a solution-based device fabrication method (for example, inkjet Printed). In this case, the hetero-form Ir(L ₁ )(L ₂ ) ₂ or Ir(L ₁ ) ₂ (L ₂ ) complex can have good stability (given by L ₁ ) and good solubility (by L ₂ given) both. The heteroconjugate complexes having an asymmetric structure may have better solution processing ability than those of a homogeneous structure having a symmetric structure due to the tendency of the asymmetric material to have a lower recrystallization. Thus, a heterologous compound can provide a device with improved manufacturing, fabrication, stability, efficiency, and/or color as compared to a homogeneous compound.

As shown in Figure 3, a hetero-compounding compound that can be advantageously used in an OLED is provided having the formula:

Wherein n = 1 or 2; R ₁ , R ₂ , R ₃ , R ₄ and R _{5 are} independently selected from the group consisting of hydrogen, alkyl and aryl, and wherein R ₁ , R ₂ , R ₃ , R ₄ and R Each of ₅ may represent a mono-, di-, tri-, tetra- or penta-substituted group; and at least one of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ is an alkyl group or an aryl group.

The present invention provides specific heterologous compounds that can be advantageously used in OLEDs:

Furthermore, a hetero-compounding compound which can be advantageously used in an OLED device is provided which has the formula: Wherein n = 1 or 2; R ₁ , R ₂ , R ₅ and R _{6 are} independently selected from the group consisting of hydrogen, alkyl and aryl; at least one of R ₁ , R ₂ , R ₅ and R ₆ is alkyl or Aryl; and R ₃ , R ₄ and R _{7 are} independently selected from the group consisting of hydrogen, alkyl and aryl, and wherein R ₃ , R ₄ and R ₇ may represent mono-, di-, tri-, tetra- or penta-substituted.

The present invention provides heterogeneous compounds that can be advantageously used in OLEDs:

Furthermore, a hetero-compounding compound which can be advantageously used in an OLED device is provided which has the formula:

Wherein n = 1 or 2; R ₁ , R ₂ , R ₅ and R _{6 are} independently selected from the group consisting of hydrogen, alkyl and aryl; at least one of R ₁ , R ₂ , R ₅ and R ₆ is alkyl or An aryl group; and R ₃ , R ₄ and R _{7 are} independently selected from the group consisting of hydrogen, alkyl and aryl, and wherein each of R ₃ , R ₄ and R ₇ may represent a single, two, three, four or Five substitutions.

The present invention provides specific heterologous compounds that can be advantageously used in OLEDs:

Furthermore, a hetero-compounding compound which can be advantageously used in an OLED device is provided which has the formula:

Wherein n = 1 or 2; R ₁ and R _{4 are} independently selected from the group consisting of hydrogen, alkyl and aryl; at least one of R ₁ and R ₄ is alkyl or aryl; and R ₂ , R ₃ and R ₅ Independently selected from the group consisting of hydrogen, alkyl and aryl, and wherein each of R ₂ , R ₃ and R ₅ may represent a mono-, di-, tri-, tetra- or penta-substitution.

The present invention provides specific heterologous compounds that can be advantageously used in OLEDs:

Furthermore, a hetero-compounding compound which can be advantageously used in an OLED device is provided which has the formula:

Wherein n = 1 or 2; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R _{6 are} independently selected from the group consisting of hydrogen, alkyl and aryl, and wherein R ₁ , R ₂ , R ₃ , R ₄ , each of R ₅ and R ₆ may represent a mono-, di-, tri-, tetra- or penta-substituted; at least one of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ is an alkyl or aryl group; R _{1 is} different from R ₄ , and R _{2 is} different from R ₅ or R _{3 is} different from R ₆ .

The present invention provides specific heterologous compounds that can be advantageously used in OLEDs:

Furthermore, a specific homogeneous compound that can be advantageously used in an OLED is provided, which has the formula:

Further, there is provided a compound wherein the compound comprises a ligand selected from the group consisting of:

Wherein the ligand is coordinated to a metal having an atomic number greater than 40. Preferably, the metal is crucible.

Further, the present invention provides an organic light-emitting device. The device includes an anode, a cathode, and an organic emission layer disposed between the anode and the cathode, the organic layer further comprising an emission dopant, wherein the compound is the emission dopant. The organic emissive layer further comprises a host material, wherein the host material is a compound comprising a carbazole group, a co-triphenyl group or a dibenzothiophene group. In particular, the host material is Compound H or Compound G.

The present invention provides a specific device in which Compound 11 or Compound 35 is the emissive dopant and Compound H or Compound G is the host material.

Specific emissive dopants for the OLED emissive layer are also provided, which can result in devices with particularly good performance. In particular, having a compound The device 25 or 26 as the emissive layer of the emissive dopant is shown in Table 1 below. The improved device stability was demonstrated using devices 25 and 26 as emitters, respectively, indicating that alkylphenyl substitution can be beneficial. Abbreviation for Cmpd.

Alkyl substitution on the 5'-phenyl group can be used to shift the evaporation temperature and stability, narrow the emission, and increase device efficiency. The heterogeneous nature of compounds 25 and 26 having only one of the substituted 2-phenylpyridines keeps the evaporation temperature low (as shown in Table 1), which is important for OLED fabrication because of the need to extend the materials Heating, and low evaporation temperatures are transferred to less thermal stress, which typically results in more complete evaporation. Alkyl substitution on the 5'-phenyl group also increases solubility (as shown in Table 1), which is critical in the fabrication of devices based on solution methods (e.g., ink jet printing). The 5' alkylphenyl group also narrows the emission and is preferred for use in OLEDs for display applications because more saturated colors can be achieved. Furthermore, the use of the devices of compounds 25 and 26 demonstrates that the use of heteroconjugates can impart high device efficiencies.

Likewise, devices having an emissive layer using heterocompatible compounds 6, 35, 11, 18 or 2 as dopants can result in devices having particularly good properties. In particular, the device has an emissive layer using Compound 6 as a dopant, an emissive layer using Compound 35 as a dopant, an emissive layer using Compound 35 as a dopant and Compound H as a host material, and Compound 35 as an admixture An impurity layer of compound G as a host material, an emission layer using compound 11 as a dopant and compound H as a host material, an emission layer using compound 11 as a dopant and compound G as a host material, and compound 18 as a compound Emissive layer of dopant, and/or emission using compound 2 as a dopant Floor. Such devices often have one or more improvements in device stability, line width, or device efficiency, as shown in Table 1.

The present invention provides a particular Ir(6-alkyl ppy) type of compound which results in a device having a particularly narrow linewidth of light. In particular, the device used a hetero-compound compound 35 or 11 as an emissive dopant as shown in Table 1. Substitution at the 6 position is believed to have this effect because it contributes to the spatial effect of the Ir complex, resulting in a relatively long N-Ir bond that is transferred to a narrower emission. Thus, the Ir(ppy) compound has a 6-alkyl group and is particularly useful for achieving narrow ray linewidths and improved device stability with heterogeneous properties without significantly increasing the evaporation temperature compared to the homogeneous counterpart.

The present invention provides a process for the preparation of an Ir(L _a )(L _b )(L _c ) complex comprising reacting an intermediate having the formula (L _a )(L _b )IrX with L _c to produce Ir(L) _a ) (L _b )(L _c ) complex, wherein L _a , L _b and L _{c are} independently a bidentate metallization ligand having the formula: Wherein R ₃ , R ₄ , R ₅ , R ₆ , R′ ₃ , R′ ₄ , R′ ₅ and R′ _{6 are} independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl a group, CN, CO ₂ R, C(O)R, NR ₂ , NO ₂ , OR, halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl or heterocyclic group; wherein R At least one of ₆ or R' ₃ is not hydrogen, and R ₆ or R' ₃ is selected from the group consisting of alkyl, alkenyl, alkynyl, alkylaryl, CN, CO ₂ R, C(O R, NR ₂ , NO ₂ , OR, halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, and heterocyclic;

Examples of the method of preparing a complex having the formula Ir(L _a )(L _b )(L _c ) include a complex of (L _a ), (L _b ) and (L _c ) photoactive.

Examples of the method of preparing a complex having the formula Ir(L _a )(L _b )(L _c ) include wherein R' ₆ is hydrogen and R ₃ is selected from an alkyl group, an alkenyl group, an alkynyl group, an alkylaryl group. a group consisting of CN, CO ₂ R, C(O)R, NR ₂ , NO ₂ , OR, halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, and heterocyclic group L _a , L _b and L _c . The yield is at least 30% or at least 50%.

Examples of the method of preparing a complex having the formula Ir(L _a )(L _b )(L _c ) include wherein R ₃ is hydrogen, and R′ _{6 is} selected from an alkyl group, an alkenyl group, an alkynyl group, an alkylaryl group, L of CN, CO ₂ R, C(O)R, NR ₂ , NO ₂ , OR, halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl and heterocyclic groups _a , L _b and L _c . The yield is at least 10%.

Examples of the method of preparing a complex having the formula Ir(L _a )(L _b )(L _c ) include those in which L _a , L _b and L _{c are the} same.

Examples of the method of preparing a complex having the formula Ir(L _a )(L _b )(L _c ) include wherein R ₆ is a methyl group and R ₃ , R ₄ , R ₅ , R′ ₃ , R′ ₄ , R′ _{Both 5} and R' ₆ are hydrogen L _a , L _b and L _c .

Examples of the method of preparing a complex having the formula Ir(L _a )(L _b )(L _c ) include wherein R' ₃ is methyl, R' ₅ is methyl, R ₄ is methyl and R ₃ , R ₅ R ₆ , R′ ₄ and R′ ₆ are all hydrogen L _a , L _b and L _c .

Examples of the method of preparing a complex having the formula Ir(L _a )(L _b )(L _c ) include wherein R' ₃ is a methyl group, R' ₅ is a methyl group, and R ₃ , R ₄ , R ₅ , R _6. R' ₄ and R' ₆ are all L _a , L _b and L _{c of} hydrogen.

As discussed in the above paragraphs, the yield of the ruthenium complex having a space-demanding ligand can be improved by a method in which the intermediate Ir(L ₂ ) ^t Buacac is reacted with L to produce IrL ₃ . For example, the Ir(L ₂ ) ^t Buacac intermediate process provides intermediate I in the synthesis of compound 17, compound 32 and compound 11 in improved yield. The reaction from Ir(L ₂ ) ^t Buacac to IrL ₃ complex is shown in Figure 4. Likewise, an improved yield of a compound having the formula Ir(L _a )(L _b )(L _c ) can be improved by reacting the intermediate Ir(L _a )(L _b ) ^t Buacac with L _c .

experiment

Some of the anthracene compounds which are optionally substituted with an alkyl group and/or an aryl group are synthesized as follows: Compound 1

Step 1. 10 g (67.5 mmol) of 2,4-dichloropyridine, 9 g (74 mmol) of phenylboronic acid, 28 g (202 mmol) of potassium carbonate, 250 ml of dimethoxy B The alkane and 150 ml of water were mixed in a 3-necked flask. The system was purged with nitrogen for 30 minutes. 2.3 g (2.0 mmol) of Pd(PPh ₃ ) _{4 was} added and the mixture was heated to reflux for 20 hours. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate and dried over magnesium sulfate. The product was subjected to column chromatography using 5% ethyl acetate and hexane. A 9.2 (72% yield) product was obtained after the column.

Step 2. 8.8 g (46 mmol) of 4-chloro-2-phenylpyridine, 7 g (69 mmol) of isobutylboronic acid, 298 g (138 mmol) of potassium phosphate, 1.5 g (3.68) Millol) 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 100 ml of toluene was mixed in a 3-necked flask. The system was purged with nitrogen for 30 minutes. 0.84 g (0.92 mmol) of Pd ₂ (dba) _{3 was} added and the mixture was heated to reflux for 4 hours. After cooling to room temperature, the reaction mixture was filtered through a pad of Celite. The product was subjected to column chromatography using 5% ethyl acetate and hexane. After the column was obtained 8.3 g of product (85% yield).

Step 3. 7.3 g (34.5 mmol) of 4-isobutyl-2-phenylpyridine and 3.4 g (6.9 mmol) of Ir(acac) ₃ were heated under reflux in 50 ml of ethylene glycol for 24 hours. After cooling to room temperature, 100 ml of methanol was added. The precipitate was collected by filtration. The solid was purified by column using 1:1 dichloromethane and hexanes as a solvent. After purification of the column, 3.1 g of product (55% yield) was obtained. The product was further purified by high vacuum sublimation at 240 °C.

Compound 2

Step 1. 2.1 g (2.6 mmol) of 4-[4-isobutyl-2-phenylpyridine]ruthenium (III) was dissolved in 100 ml of dichloromethane. To this solution was added dropwise 0.45 g (2.6 mmol) of N-bromosuccinimide in dichloromethane. After stirring at room temperature overnight, the reaction was concentrated to 50 mL solvent and precipitated from methanol. The solid was dried under vacuum and used in the next step without further purification. 2.1 grams of product was collected which contained 71% monobrominated compound.

Step 2. Add 2.1 grams of the ruthenium bromide complex mixture from step 1, 1.2 grams (4.6 millimoles) of pentamidine diboron, 0.68 grams (6.9 millimoles) of potassium acetate, 100 milliliters of dioxane at 3 necks Mix in the flask. The system was purged with nitrogen for 30 minutes. To the mixture was added 0.06 g (0.07 mmol) of Pd(dppf) ₂ Cl ₂ . The reaction was heated at 90 ° C for 15 hours. The reaction was monitored by TLC. After the reaction was completed, the solvent was evaporated. The residue was purified by column chromatography using 1:1 dichloromethane and hexane. 1.1 g of product was obtained.

Step 3. 1.1 g (1.16 mmol) of borate, 0.55 g (3.5 mmol) of bromobenzene, 0.8 g (3.48 mmol) of potassium phosphate, 0.02 g (0.046 mmol) of 2-bicyclic Hexylphosphino-2',6'-dimethoxybiphenyl, 60 ml of toluene and 6 ml of water were mixed in a 3-necked flask. The system was purged with nitrogen for 30 minutes. 0.01 g (0.01 mmol) of Pd ₂ (dba) _{3 was} added and the mixture was heated to reflux for 4 hours. After cooling to room temperature, the reaction mixture was filtered through a pad of Celite. The product was purified by column chromatography using 1:1 dichloromethane and hexane. 1.0 g of product was obtained after the column. The product was further purified by high vacuum sublimation at 260 °C.

Compound 3

Step 1. Dissolve bis(4-methyl-2-phenylpyridine) ruthenium (III) (1.3 g, 1.9 mmol), N -bromosuccinimide (0.33 g, 1.9 mmol) in 400 In milliliters of dichloromethane. The mixture was purged with nitrogen for 10 minutes and stirred at room temperature overnight in the dark. The solvent was evaporated under reduced pressure. The residue was washed with methanol. A mixture of 1.4 g (95% yield) of a yellow solid was obtained.

Step 2. The brominated Ir complex mixture from step 1 (1.3 grams, 1.7 millimoles), pentamidine diboron (0.85 grams, 3.4 millimoles), potassium acetate (0.5 grams, 5.1 millimoles) Mix with anhydrous dioxane (100 mL) and purge with nitrogen for 15 minutes. Then Pd(dppf) ₂ Cl ₂ (42 mg, 0.05 mmol) was added and the mixture was again purged with nitrogen for 10 min. After heating at 90 ° C overnight, the mixture was cooled to room temperature and evaporated under reduced pressure. The crude product was purified by silicon dioxide column using ₂ Cl ₂ in hexanes CH at most 30%, as a yellow solid was obtained 0.9 g (64% yield).

Step 3. The product from Step 2, bromobenzene (0.41 g, 2.6 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (14.4 mg, 0.035 mmol) ), tripotassium phosphate (557 mg, 2.6 mmol), toluene (60 ml) and water (20 ml) were combined and purged with nitrogen for 15 minutes. Then Pd ₂ (dba) _{3 was} added and the mixture was purged again with nitrogen for 10 minutes. After refluxing overnight, the organic layer was collected and dried using MgSO ₄ . Purified and 1 CH ₂ Cl ₂ in hexanes to give 0.6 g as a yellow solid (89% yield): The crude product by silicon dioxide column using 1. The product was further purified by high vacuum sublimation at 260 °C.

Compound 4

Step 1. 2,4-Dichloropyridine (10 g, 67.6 mmol), biphenyl-3-ylboronic acid (13.4 g, 67.6 mmol), palladium acetate (0.5 g, 2 mmol), Triphenylphosphine (2.1 g, 8.1 mmol), potassium carbonate (28 g, 203 mmol), dimethoxyethane 120 ml and water 40 ml were mixed in a 300 ml 3-necked flask. The system was purged with nitrogen for 15 minutes and then refluxed overnight. After the reaction was cooled to room temperature, the organic layer was collected, dried over MgSO ₄ Gan sulfate and evaporated under reduced pressure. The crude product was purified by chromatography eluting with EtOAc EtOAc (EtOAc)

Step 2. 2-(Biphenyl-3-yl)-4-chloropyridine (12.2 g, 45.9 mmol), isobutylboronic acid (5.6 g, 55.1 mmol), tripotassium phosphate (29 g, Mix 138 mmol, toluene (300 mL). The system was purged with nitrogen for 15 minutes. Then 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.8 g, 1.8 mmol) and Pd ₂ (dba) ₃ (0.4 g, 0.5 mmol) were added. The system was purged again with nitrogen for 5 minutes. After refluxing overnight, the reaction was cooled to room temperature and washed with water. The organic layer was combined dry Gan MgSO ₄ and evaporated under reduced pressure. The crude product was purified by chromatography eluting with EtOAc EtOAc EtOAc (EtOAc)

Step 3. 2-(Biphenyl-3-yl)-4-isobutylpyridine (1 g, 3.5 mmol), Ir(acac) ₃ (0.4 g, 0.9 mmol) and ethylene glycol ( 10 ml) mixed. The system was evacuated and refilled with nitrogen for 3 times. After heating at 220 ° C (sand bath temperature) overnight, the reaction was cooled to room temperature. The yellow precipitate was collected by filtration and washed with methanol. The crude product was purified by EtOAc (EtOAc) eluting The product was further purified by high vacuum sublimation at 280 °C.

Compound 5

Step 1. 2-Bromo-5-chloropyridine (12.0 g, 62.3 mmol), biphenyl-3-ylboronic acid (14.9 g, 75 mmol), palladium acetate (0.035 g, 2.5 mol%) Triphenylphosphine (0.8 g, 5 mol%) and potassium carbonate (26.0 g, 188 mmol) were placed in a 500 ml 3-neck flask. 150 ml of dimethoxyethane and 150 ml of H ₂ O were added to the flask. Nitrogen gas was purged through the solution for 30 minutes and then the solution was refluxed for 8 hours under a nitrogen atmosphere. The reaction was then cooled to room temperature and the organic phase was separated from the aqueous phase. The aqueous phase was washed with EtOAc and EtOAc was evaporated and evaporated. The product was chromatographed using a cerium oxide gel using ethyl acetate and hexane as a solvent. The solvent was removed to give 14.5 g of a white solid (yield: 88%).

Step 2. 2-(Biphenyl-3-yl)-5-chloropyridine (5.0 g, 19.0 mmol), isobutylboronic acid (4.0 g, 0.38 mmol), Pd ₂ (dba) ₃ ( 0.20 g, 1 mol%), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.31 g, 4 mol%), potassium phosphate monohydrate (13 g, 57 m Mohr) was mixed in 100 ml of toluene in a 250 ml round bottom flask. Nitrogen gas was purged through the solution for 20 minutes and the mixture was refluxed overnight under a nitrogen atmosphere. The reaction mixture was cooled and the solvent was removed in vacuo. The crude product was chromatographed using a cerium oxide gel column using 2% ethyl acetate in hexanes as a solvent. The solvent was then removed under vacuum to give 4 g of product.

Step 3. 2-(Biphenyl-3-yl)-5-isobutylpyridine (4.0 g, 14.0 mmol) and Ir(acac) ₃ (1.7 g, 3.5 mmol) and 10 mL of Ethylene The alcohol was placed in a 100 ml round bottom flask. The reaction mixture was refluxed at 220 ° C under a nitrogen atmosphere overnight. The reaction mixture was allowed to cool and 10 mL of methanol was added to the mixture. The precipitate was filtered and washed with methanol. The product was chromatographed using a ceria gel column using dichloromethane and hexane (50:50) as a solvent. 1.3 g of product were obtained (36% yield).

Compound 6

Step 1. 2-Bromo-5-methylpyridine (100 g, 581 mmol), phenylboronic acid (85.2 g, 700 mmol), palladium acetate (0.4 g, 2.5 mol%), triphenyl A mixture of phosphine (7.6 g, 5 mol%) and potassium carbonate (240.0 g, 1740 mmol) in 600 ml of dimethoxyethane and 600 ml of water was purged with nitrogen for 30 minutes and heated to reflux under nitrogen. 8 hours. The reaction was then cooled to room temperature and the organic phase was separated from the aqueous phase. The aqueous phase was washed with EtOAc and EtOAc was evaporated and evaporated. The product was subjected to column chromatography using a ceria gel using ethyl acetate and hexane as an eluent. The solvent was removed to give 90.0 g of a clear liquid (92% yield).

Step 2. Place 2-phenyl-5-methylpyridine (10.0 g, 59.0 mmol) and Ir(acac) ₃ (10.0 g, 20.4 mmol) and 20 mL of ethylene glycol in a 100 ml round bottom. In the flask. The reaction mixture was refluxed at 220 ° C under a nitrogen atmosphere overnight. The reaction mixture was allowed to cool and 10 mL of methanol was added to the mixture. The precipitate was filtered and washed with methanol. The product was subjected to column chromatography using a ceria gel column using dichloromethane and hexane (50:50) as a solution. 5.94 g of product were obtained (42% yield).

Step 3. Indole (2-phenyl-4-methylpyridine) ruthenium (III) (4.4 g, 5.4 mmol) was dissolved in 600 mL of dichloromethane. N-bromosuccinimide (0.96 g, 5.4 mmol) was added dropwise to dichloromethane over a period of 15 min. The reaction mixture was stirred at room temperature for 2 hours. The reaction volume was reduced to 200 ml and 200 ml of ethanol was added to precipitate the product. The solid was filtered and air dried overnight and used in the next step without further purification. 4.8 grams of product was collected which contained about 71% monobrominated compound.

Step 4. Bring the bromination mixture from step 3 (5.0 g, 6.5 mmol), pentamidine diboron (3.27 g, 12.9 mmol), potassium acetate (2.0 g, 20 mmol) and 200 ml two The methane was mixed in a 3-necked flask. The system was purged with nitrogen for 30 minutes. Then Pd(dppf) ₂ Cl ₂ (0.16 g, 3 mol%) was added. The reaction was heated at 90 ° C for 15 hours. After the reaction was completed, the solvent was evaporated. The residue was subjected to column chromatography using a cerium oxide gel column using 1:1 dichloromethane and hexane as a solvent, followed by 60:40 dichloromethane and hexane. 1.9 g of product was obtained.

Step 5. Irr borate (2.2 g, 2.7 mmol), bromobenzene (0.85 g, 5.4 mmol), potassium phosphate (1.86 g, 8.1 mmol), 2-dicyclohexylphosphino- 2',6'-Dimethoxybiphenyl (0.06 g, 5 mol%), 100 ml of toluene and 10 ml of water were mixed in a 3-necked flask. The system was purged with nitrogen for 30 minutes. Pd ₂ (dba) ₃ (0.02 g, 1 mol %) was added to the reaction mixture, which was then refluxed for 2 hours. The reaction was cooled to room temperature and filtered through a pad of Celite. The residue was subjected to column chromatography using a cerium oxide gel column using 1:1 dichloromethane and hexane as a solvent. 1.5 g of product was obtained.

Compound 7

Step 1. 2-Bromo-5-chloropyridine (15.0 g, 77.94 mmol), phenylboronic acid (11.4 g, 93.53 mmol), triphenylphosphine (2.04 g, 7.79 mmol) A mixture of potassium carbonate (26.9 g, 194.9 mmol) in 150 ml of dimethoxyethane and 100 ml of water was purged with nitrogen for 20 min. Palladium acetate (0.87 g, 3.90 mmol) was added and the reaction mixture was heated to reflux under nitrogen overnight. The reaction mixture was cooled and filtered through celite. The diatomaceous earth was washed with water and ethyl acetate. The layers were separated and the aqueous layer was extracted with EtOAc. The organic layer was dried over magnesium sulfate, filtered and evaporated to yield The residue was purified by column chromatography using 0 to EtOAc ethyl acetate /hexane. 11.8 g (80% yield) of a white solid was obtained.

Step 2. 2-Phenyl-5-chloropyridine (11.8 g, 62.22 mmol), isobutylboronic acid (12.7 g, 124.44 mmol), 2-dicyclohexylphosphino-2', 6' a mixture of dimethoxybiphenyl (1.02 g, 2.49 mmol) and tripotassium phosphate (39.62 g, 186.66 mmol) in 300 ml of toluene and 100 ml of water was purged with nitrogen for 20 minutes, after which Pd ₂ was added. (dba) ₃ (0.57 g, 0.62 mmol). The mixture was refluxed under nitrogen overnight. The cooled mixture was filtered through celite and the celite was washed with water and ethyl acetate. The layers were separated and the aqueous layer was extracted with EtOAc. The organic layer was dried over magnesium sulfate, filtered and evaporated to yield The residue was purified by column chromatography using EtOAc (EtOAc)EtOAc. 11.05 g (84% yield) of a white solid was obtained.

Step 3. A mixture of 2-phenyl-5-isobutylpyridine (6.86 g, 32.47 mmol) and Ir(acac) ₃ (3.16 g, 6.46 mmol) in 100 mL of ethylene glycol at 210 Heat at °C overnight. The reaction was cooled and methanol was added and a yellow solid was filtered. The solid was purified by column chromatography using 20 and 40% dichloromethane/hexanes. 3.4 g (64% yield) of product was obtained.

Compound 8

Step 1. 2-Bromo-5-chloropyridine (15.0 g, 77.94 mmol), phenylboronic acid (11.4 g, 93.53 mmol), triphenylphosphine (2.04 g, 7.79 mmol) and carbonic acid A mixture of potassium (26.9 g, 194.9 mmol) in 150 ml of dimethoxyethane and 100 ml of water was purged with nitrogen for 20 min. Palladium acetate (0.87 g, 3.90 mmol) was added and the reaction mixture was heated to reflux under nitrogen overnight. The reaction mixture was cooled and filtered through celite. The diatomaceous earth was washed with water and ethyl acetate. The layers were separated and the aqueous layer was extracted with EtOAc. The organic layer was dried over magnesium sulfate, filtered and evaporated to yield The residue was purified by column chromatography using 0 to EtOAc ethyl acetate /hexane. 11.8 g (80% yield) of a white solid was obtained.

Step 2. 2-Phenyl-5-chloropyridine (11.8 g, 62.22 mmol), 2-methylpropylboronic acid (12.7 g, 124.44 mmol), 2-dicyclohexylphosphino-2' , a mixture of 6'-dimethoxybiphenyl (1.02 g, 2.49 mmol), tripotassium phosphate (39.62 g, 186.66 mmol) in 300 ml of toluene and 100 ml of water was purged with nitrogen for 20 minutes, after which Pd ₂ (dba) ₃ (0.57 g, 0.62 mmol) was added. The mixture was refluxed under nitrogen overnight. The cooled mixture was filtered through a pad of celite and washed with water and ethyl acetate. The layers were separated and the aqueous layer was extracted with EtOAc. The organic layer was dried over magnesium sulfate, filtered and evaporated to yield The residue was purified by column chromatography using EtOAc (EtOAc)EtOAc. 11.05 g (84% yield) of a white solid was obtained.

Step 3. A mixture of 2-phenyl-5-isobutylpyridine (6.86 g, 32.47 mmol) and Ir(acac) ₃ (3.16 g, 6.46 mmol) in 100 mL of ethylene glycol at 210 Heat at °C overnight. The reaction was cooled and methanol was added and a yellow solid was filtered. The solid was purified by column chromatography using 20 &lt;RTI ID=0.0&gt;&gt;

Step 4. Indole (2-phenyl-4-isobutylpyridine) ruthenium (III) (4.5 g, 6.5 mmol) was dissolved in 600 mL of dichloromethane. N-bromosuccinimide (1.16 g, 6.5 mmol) in dichloromethane was added dropwise over a period of 15 minutes. The reaction mixture was stirred at room temperature for 2 hours. The reaction volume was reduced to 200 ml and 200 ml of ethanol was added to precipitate the product. The solid was filtered and air dried overnight and used in the next step without further purification. 4.9 grams of product was collected which contained about 71% monobrominated compound.

Step 5. The brominated mixture (4.8 g, 5.3 mmol), pentamidine diboron (2.71 g, 18.7 mmol), potassium acetate (1.6 g, 16.3 mmol) and 200 ml of dioxane in 3 Mix in a neck flask. The system was purged with nitrogen for 30 minutes. Then Pd(dppf) ₂ Cl ₂ (0.43 g, 0.53 mmol) was added. The reaction was heated at 90 ° C for 15 hours. After the reaction was completed, the solvent was evaporated. The residue was chromatographed using a ruthenium dioxide gel column using 1:1 dichloromethane and hexane as a solvent, followed by 60:40 dichloromethane and hexane to give 1.0 g of product.

Step 6. Irr borate (0.9 g, 0.9 mmol), bromobenzene (0.70 g, 4.7 mmol), potassium phosphate (1.96 g, 8.2 mmol), 2-dicyclohexylphosphino- 2',6'-Dimethoxybiphenyl (0.19 g, 5 mol%), 100 ml of toluene and 10 ml of water were mixed in a 3-necked flask. The system was purged with nitrogen for 30 minutes. Pd ₂ (dba) ₃ (0.01 g, 1 mol %) was added to the reaction mixture, which was then refluxed for 2 hours. The reaction was cooled to room temperature and filtered through a pad of Celite. The residue was chromatographed using a cerium oxide gel column using 1:1 dichloromethane and hexane as a solvent. 0.5 g of product was obtained.

Compound 9

Step 1. 2-Bromo-6-methylpyridine (10.0 g, 58.0 mmol), 3-methylphenylboronic acid (9.3 g, 70 mmol), palladium acetate (0.6 g, 5 mol%) Triphenylphosphine (1.5 g, 10 mol%) and potassium carbonate (32.0 g, 232 mmol) were placed in a 500 ml 3-neck flask. 100 ml of dimethoxyethane and 100 ml of H ₂ O were added to the flask. A nitrogen purge was passed through the solution for 20 minutes and then the solution was refluxed for 8 hours under a nitrogen atmosphere. The reaction was then cooled to room temperature and the organic phase was separated from the aqueous phase. The aqueous phase was washed with EtOAc and EtOAc was evaporated and evaporated. The product was chromatographed using a cerium oxide gel using ethyl acetate and hexane as a solvent. The solvent was removed to give 8.08 g (yield: 76% yield).

Step 2. Dissolve 2-(5-methylphenyl)-6-methylpyridine (10.0 g, 54.6 mmol) and IrCl ₃ (7.8 g, 21.8 mmol) in a 250 mL round bottom flask. A 3:1 mixture of 2-ethoxyethanol in water corresponding to water. A nitrogen purge was passed through the solution for 10 minutes and then refluxed under nitrogen for 16 hours. The reaction mixture was cooled to room temperature and the precipitate was filtered and washed with methanol. The dimer was then dried under vacuum and used in the next step without further purification. After vacuum drying, 8.6 g of dimer was obtained.

Step 3. Add the dimer (6.0 g, 5 mmol), 2,4-pentanedione (1.5 g, 15.0 mol) and potassium carbonate (7.0 g, 50.0 mmol) to 200 m. Add 2-methoxyethanol and reflux overnight. The solvent was removed on a rotary evaporator and the solid was redissolved in dichloromethane and chromatographed using a silica gel column and dichloromethane and hexanes as a solvent. The solvent was removed on a rotary evaporator and the product was washed with methanol and dried to yield 5.1 g.

Step 4. The product from Step 3 (2.0 g, 3 mmol), 2-(3-methylphenyl)-6-methylpyridine (3.4 g, 6 mole equivalents) and potassium carbonate (2.5 g) , 18 mmol) placed in a 100 ml round bottom flask. The reaction mixture was heated at 250 ° C for 8 hours. The reaction mixture was allowed to cool and 10 mL of methanol was added to the mixture. The precipitate was filtered and washed with methanol. The product was chromatographed using a ceria gel column using dichloromethane and hexane (50:50) as the eluent. 1.1 g of product were obtained (50% yield).

Compound 10

Step 1. Preparation of 2-chloro-6-methylpyridine (4.1 g, 32.4 mmol), biphenyl- 3-ylboronic acid (7.7 g, 38.9 mmol), triphenylphosphine (0.85 g, 3.24 mmol), and potassium carbonate (11.2 g, 81.0 mmol) in 60 ml of dimethoxyethane and A mixture of 40 ml of water. Nitrogen gas was introduced into the mixture for 20 minutes. Palladium acetate (0.36 g, 1.62 mmol) was added and the reaction mixture was heated to reflux under nitrogen overnight. The reaction was cooled and diluted with water and ethyl acetate. The layers were separated and the aqueous layer was extracted with EtOAc. The organic layer was dried over magnesium sulfate, filtered and evaporated to yield The residue was purified by column chromatography using 0, 1 and 2% ethyl acetate / hexanes. 6.9 g (87% yield) of a clear liquid was obtained.

A mixture of Ir dimer (2.0 g, 1.87 mmol) in 200 ml of dichloromethane and 10 ml of methanol was prepared. Silver triflate (1.0 g, 3.92 mmol) was added and the reaction mixture was stirred for 3 h. The green solid was filtered off and washed with a small portion of dichloromethane. The filtrate was evaporated to dryness and dried under high vacuum. The material was transferred to a 100 mL flask and the product from Step 1 (1.8 g, 7.48 mmol) was then added, followed by 15 mL of tridecane. The mixture was heated at 190 °C overnight. Four compounds are formed. The green solid was filtered off and purified by column chromatography using 10, 20, 40 and 50% dichloromethane/hexanes. 0.80 g of crude compound 34 was obtained which was further purified by column chromatography, recrystallization from toluene and sublimation to afford 0.26 g.

Compound 11

Step 1. 2-Bromo-6-methylpyridine (100.0 g, 580 mmol), phenylboronic acid (80.0 g, 640 mmol), palladium acetate (3.3 g, 2.5 mol%), triphenyl a mixture of phosphine (8.0 g, 5 mol%) and potassium carbonate (240 g, 1740 mmol) in 600 ml of dimethoxyethane and 600 ml of water was purged with nitrogen for 30 minutes and then the solution was made nitrogen. Under reflux for 8 hours. The reaction was then cooled to room temperature and the organic phase was separated from the aqueous phase. The aqueous phase was washed with EtOAc and EtOAc was evaporated and evaporated. will The product was subjected to column chromatography using a cerium oxide gel using ethyl acetate and hexane as an eluent. The solvent was removed to give 90.5 g of a clear liquid (92% yield).

Step 2. Dissolve 2-phenyl-6-methylpyridine (24.0 g, 142 mmol) and cerium (III) chloride (20.0 g, 56.8 mmol) in a 500 ml round bottom flask in 250 ml. a 3:1 mixture of 2-ethoxyethanol and water. The mixture was purged with nitrogen for 10 min and then refluxed under nitrogen for 16 h. The reaction mixture was cooled to room temperature and the precipitate was filtered and washed with methanol. The dimer was then dried under vacuum and used in the next step without further purification. After drying in vacuo, 16.0 g of dimer (50% yield) was obtained.

Step 3. Add the dimer (15.0 g, 13.3 mmol), dipentamethylene methane (25.0 g, 133 mmol), and potassium carbonate (18.0 g, 133 mmol) to 250 mL. It was refluxed in 1,2-dichloroethane for 24 hours. The reaction mixture was cooled and the solvent was removed in vacuo. The residue was subjected to column chromatography using a triethylamine-pretreated ceria gel. Methylene chloride and hexane (1:1) were used as the eluent. 17.8 g (94% yield) of product was obtained.

Step 4. A mixture of the Ir complex (10.0 g, 14.0 mmol) was placed in a 100 mL round bottom flask. 2-Phenyl-6-methylpyridine (23.0 g, 1360 mmol) and sodium carbonate (7.7 g, 70.0 mmol) were heated in a sand bath (sand temperature 300 ° C) under nitrogen for 24 hours. The reaction was then allowed to cool and methanol was added. The mixture was filtered and washed with methanol. The crude product was dissolved in dichloromethane and passed through a ceria gel plug. The solvent was removed and the product was washed with methanol and then dried to give 7.2 g (yield: 74%).

Step 5. Indole (2-phenyl-6-methylpyridine) ruthenium (III) (5.0 g, 7.2 mmol) was dissolved in 1 liter of dichloromethane. N-bromosuccinimide (2.6 g, 15.6 mmol) in dichloromethane was added dropwise over a period of 15 minutes. The reaction mixture was stirred at room temperature for 2 hours. The reaction volume was reduced to 200 ml and 200 ml of ethanol was added to precipitate the product. The solid was filtered and air dried overnight and used in the next step without further purification. 6.0 grams of product was collected which contained about 71% monobrominated compound.

Step 6. The brominated mixture (6.2 g, 7.3 mmol), pentamidine diboron (7.38 g, 29 mmol), potassium acetate (2.14 g, 21.8 mmol) and 300 mL of dioxane at Mix in a 3-neck flask. The system was purged with nitrogen for 30 minutes. Pd(dppf) ₂ Cl ₂ (0.60 g, 0.74 mmol) was then added to the reaction mixture. The reaction was heated at 90 ° C for 15 hours. After the reaction was completed, the solvent was evaporated. The residue was chromatographed using a cerium oxide gel column using 1:1 dichloromethane and hexane as the eluent followed by 60:40 dichloromethane and hexane. 0.8 g of product was obtained.

Step 7. Ion borate (0.8 g, 0.8 mmol), bromobenzene (1.32 g, 8.4 mmol), potassium phosphate (5.0 g, 21.7 mmol), 2-dicyclohexylphosphino- A mixture of 2',6'-dimethoxybiphenyl (0.30 g, 10 mol%) in 100 ml of toluene and 10 ml of water was purged with nitrogen for 30 min. Pd ₂ (dba) ₃ (0.08 g, 2 mol %) was added to the reaction mixture, which was then refluxed for 2 hours. The reaction was allowed to cool to room temperature and was filtered thru a pad of Celite using a silica gel column using 1:1 dichloromethane and hexane as a solvent. 0.7 g of product was obtained.

Compound 12

Step 1. 2,6-Dichloropyridine (25.0 g, 169 mmol), phenylboronic acid (22.7 g, 186 mmol), palladium acetate (0.9 g, 2.5 mol%), triphenylphosphine (2.2 g, 5 mol%) and a mixture of potassium carbonate (70.0 g, 507 mmol) in 300 ml of dimethoxyethane and 300 ml of water were purged with nitrogen for 30 minutes and then the solution was refluxed under nitrogen. 8 hours. The reaction was then cooled to room temperature and the organic phase was separated from the aqueous phase. The aqueous phase was washed with EtOAc and EtOAc was evaporated and evaporated. The product was subjected to column chromatography using a ceria gel using ethyl acetate and hexane as an eluent. The solvent was removed to give 12.0 g of a white solid (yield: 38%).

Step 2. 2-Phenyl-6-chloropyridine (12.0 g, 63.0 mmol), isobutylboronic acid (19.5 g, 190 mmol), Pd ₂ (dba) ₃ (0.60 g, 1 mol) %), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.8 g, 3 mol%), potassium phosphate monohydrate (40.0 g, 189 mmol) in 200 ml The mixture in toluene was purged with nitrogen in a 500 mL round bottom flask for 20 min and the mixture was refluxed overnight under nitrogen. The reaction mixture was cooled and the solvent was removed in vacuo. The crude product was chromatographed using a cerium oxide gel column using 2% ethyl acetate in hexanes as a solvent. The solvent was then removed under vacuum to give 12 g of product.

Step 3. 2-Phenyl-6-isobutylpyridine (5.0 g, 23.7 mmol) and cerium (III) chloride (2.08 g, 5.6 mmol) in 50 mL of 2-ethoxyethanol and The mixture in a 3:1 mixture of water was purged with nitrogen for 10 minutes and then refluxed under nitrogen for 16 hours. The reaction mixture was cooled to room temperature and the precipitate was filtered and washed with methanol. The dimer was then dried under vacuum and used in the next step without further purification. After vacuum drying, 3.0 g of dimer (40% yield) was obtained.

Step 4. The dimer (2.5 g, 1.9 mmol) was dissolved in 200 mL of dichloromethane in a 500 mL round bottom flask. A solution of silver triflate (1.0 g, 3.9 mmol) in 10 mL of methanol was added to the dimer solution. The reaction mixture was stirred overnight. The mixture was filtered and the filtrate evaporated to give 2.9 g of desired material.

Step 5. Tritium triflate (1.0 g, 1.3 mmol) and 2-(biphenyl-3-yl)pyridine (0.9 g, 3.4 mmol) were placed in a 100 mL round bottom flask. 10 ml of ethanol was added to the flask. The mixture was purged with nitrogen for 10 min and then refluxed under nitrogen for 16 h. The reaction was allowed to cool to room temperature and isopropanol was added to precipitate the product. The reaction mixture was filtered and the residue was chromatographed using EtOAc m. 0.7 g of product was obtained.

Compound 13

Step 1. 100 g (0.94 mol) of 3,4-dimethylpyridine and 40 g (1.0 mol) of sodium amination were added to 240 ml of N,N -dimethylaniline. The reaction mixture was heated at 150 ° C for 7 hours while stirring under nitrogen. After cooling, the reaction mixture was added to 400 ml of ice water. The mixture was extracted with ethyl acetate. The organic phase is concentrated and fractionally distilled. 40 g (35% yield) of 2-amino-3,4-dimethylpyridine (about 78% by GC) and 2-amino-4,5-lutidine (by GC about 22) were obtained. A white solid mixture of %) which was used in the next step without further purification.

Step 2. A 8.0 g (0.065 mol) step 1 mixture was added to about 25 mL of 60% HBr and then stirred at -15 °C to -17 °C. 31.0 g of pre-cooled (about 0 ° C) Br ₂ (0.2 mol) was added dropwise and the mixture was stirred for 20 minutes. A pre-cooled (0 ° C) NaNO ₂ solution of 11.4 g (0.16 mol) of NaNO ₂ dissolved in 20 ml of water was added dropwise to the reaction mixture at -15 ° C to -17 ° C. After the addition, the reaction was stirred for 1 hour. Slowly add ice-cold 25% NaOH solution until the solution becomes alkaline. The mixture was extracted with ethyl acetate. The organic extract was concentrated and distilled under vacuum. A solid mixture of 10.7 g (88% yield) of 2-bromo-3,4-dimethylpyridine (about 78%) and 2-bromo-4,5-lutidine (about 22%) was obtained. It was used in the next step after purification.

Step 3.30.0 g (162 mmol) Step 2 Mixture, 34.0 g (167 mmol) 3-bromophenylboronic acid, 5.0 g (4.3 mmol) Pd(PPh ₃ ) ₄ , 60 g (434 mil Mo) K ₂ CO ₃ , 130 ml DME and 130 ml water. The reaction mixture was refluxed for 20 hours and the organic extract was purified by using a cerium oxide gel column using 10% ethyl acetate in hexane solvent as a solvent, followed by distillation. The two isomers were further separated by recrystallization from hexane.

Step 4. 1.7 g (6.5 mmol) of 2-(3-bromophenyl)-3,4-dimethylpyridine, 1.2 g (7.8 mmol) of 3,5-dimethylphenylboronic acid, 235 mg (0.203 mmol) of Pd(PPh ₃ ) ₄ , 2.8 g (20.2 mmol) of K ₂ CO ₃ , 50 ml of DME and 50 ml of water were placed in a 200 ml flask and heated to reflux under nitrogen overnight. The organic extract was purified by using a methylene chloride gel column using dichloromethane as a solution. 1.5 g (81% yield) of product was obtained.

Step 5. 4.1 grams (14.2 millimoles) of the ligand from step 4, 1.4 grams (2.86 millimoles) of Ir(acac) _{3 were} added to the Schlenk tube. The tube was heated at 250 ° C for 30 hours. The reaction residue was purified by a cerium oxide gel column. 2.2 g (66% yield) of product was obtained.

Compound 14

Step 1. 3.0 g (11.4 mmol) of 2-(3-bromophenyl)-3,4-dimethylpyridine from Step 3 of Compound 36, 1.8 g (12.8 mmol) of 4-fluorobenzene Boric acid, 0.4 g (0.34 mmol) Pd(PPh ₃ ) ₄ , 4.8 g (34.7 mmol), K ₂ CO ₃ , 100 mL DME and 100 ml water were filled in a 500 ml flask and heated under nitrogen. Reflux overnight. The reaction mixture was purified by using a ceria gel column using dichloromethane as a solution. 2.5 g (80% yield) of product was obtained.

Step 5. 2.3 grams (8.3 millimoles) of the ligand from step 1, 1.02 grams (2.08 millimoles) of Ir(acac) _{3 was} added to the Schlenk tube. The tube was heated at 250 ° C for 30 hours. The reaction residue was purified by a cerium oxide gel column. 1.3 g (63%) of a solid product was obtained.

Compound 15

Step 1. 20.0 g (107.5 mol) of the mixture from step 36 of compound 36, 17.7 g (129 mmol) of 3-methylphenylboronic acid, 3.7 g (3.2 mol) (PPh ₃ ) ₄ , 44 g (0.321 mol) K ₂ CO ₃ , 100 ml DME and 100 ml water were mixed and refluxed for 20 hours. The organic extract was purified by using a cerium oxide gel column using 10% ethyl acetate in hexane as a solution. 5.1 g of 2-(3-methyl)-4,5-lutidine were obtained as confirmed by NMR and GCMS.

Step 2. 4.95 g (25.1 mmol) of the ligand from step 1, 2.7 g (5.57 mmol) of Ir(acac) ₃ and 40 ml of ethylene glycol were filled in a 200 ml flask and heated under nitrogen. Reflux overnight. The reaction residue was purified by using a methylene chloride gel column using dichloromethane as a solution. 2.6 g (60% yield) of product was obtained.

Compound 16

Step 1. Concentrated sulfuric acid (27 mL) was dissolved in 160 mL water and cooled to 0 °C. 4,6-Dimethyl-2-amino-pyridine (25 g, 205 mmol) was then added to the solution. A solution of sodium nitrite (18.4 g, 266 mmol) in 40 ml of water was then added slowly (control temperature below 5 °C). After all the sodium nitrite was added, the mixture was stirred at 0 ° C for 45 minutes and then at 95 ° C for 15 minutes. After the reaction mixture was cooled to room temperature, the pH was adjusted to a range of 6.5-7.0 using 50% w/w NaOH/water. The precipitate was collected by filtration and redissolved in dichloromethane. The aqueous filtrate was extracted with dichloromethane. The organic extracts were combined and dried over MgSO ₄ Gan dry. The solvent was evaporated under reduced pressure. The crude product was recrystallized from EtOAc (EtOAc:EtOAc)

Step 2. 4,6-Dimethylpyridin-2-ol (17 g, 138 mmol) was dissolved in 300 mL of pyridine. The mixture was cooled to -10 °C by an acetone/ice bath. The reaction was maintained under nitrogen by bubbling nitrogen through the solution. Trifluoromethanesulfonic anhydride (47 g, 28 mL, 166 mmol) was added. The mixture was stirred at 0 °C for 1 hour and then poured into 300 mL of saturated aqueous sodium bicarbonate (some gas was evaporated). The mixture was extracted with dichloromethane. The organic extracts were combined and concentrated under reduced pressure Gan dry over MgSO ₄ to give 33 g brown oil (94% yield). The crude product was used in the next step without further purification.

Step 3. 4,6-Dimethylpyridin-2-yl trifluoromethanesulfonate (18.8 g, 74 mmol), phenylboronic acid (10.8 g, 88 mmol), tripotassium phosphate (56) Grams, 264 mmol, toluene (550 ml) and water (55 ml) were combined in a 1 liter 3-neck flask. The system was purged with nitrogen for 15 minutes, then Pd ₂ (dba) ₃ (0.81 g, 0.88 mmol) and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (1.45 g) were added. , 3.5 millimoles). The system was purged again with nitrogen for 10 minutes and then refluxed for 4 hours. After the reaction was cooled to room temperature, the organic layer was collected, dried over MgSO ₄ Gan sulfate and evaporated under reduced pressure. The crude product was purified by EtOAc EtOAc (EtOAc) eluting

Step 4. Fill 2.0 g (10.9 mmol) of step 3 ligand and 1.1 g (2.2 mmol) of Ir(acac) ₃ in a Schlenk tube and heat at 250 ° C for 20 hours while stirring under nitrogen. . The reaction residue was purified by using a ceria gel column using 50% of dichloromethane in hexane as a solution. 0.6 g (34% yield) of product was obtained.

Compound 17

Step 1. 4,6-Dimethylpyridin-2-yl trifluoromethanesulfonate (18.8 g, 74 mmol), m-tolylboronic acid (12 g, 88 mmol), tripotassium phosphate (56 g, 264 mmol), toluene (550 ml) and water (55 ml) were mixed in a 1 liter 3-neck flask. The system was purged with nitrogen for 15 minutes, then Pd ₂ (dba) ₃ (0.81 g, 0.88 mmol) and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (1.45 g) were added. , 3.5 millimoles). The system was purged again with nitrogen for 10 minutes and then refluxed for 4 hours. After the reaction was cooled to room temperature, the organic layer was collected, dried over MgSO ₄ Gan sulfate and evaporated under reduced pressure. The crude product was purified by EtOAc (EtOAc) eluting

Step 2. The product of Step 1 (10 g, 50.6 mmol), cesium chloride (4.4 g, 12.6 mmol), 2-ethoxyethanol (180 mL) and water (60 mL) in 500 mL Mix in a 3-neck flask. The system was purged with nitrogen for 15 minutes and then refluxed overnight. After the reaction was cooled to room temperature, the solvent was evaporated under reduced pressure. The residue was washed with methanol to give 3.7 g, m.

Step 3. The dimer (2.7 g, 2.2 mmol), dipentamethylene methane (4.0 g, 4.5 mL, 21.6 mmol), sodium carbonate (2.3 g, 21.6 mmol) and 2 Ethoxyethanol (100 ml) was mixed in a 300 ml 3-necked flask. The system was purged with nitrogen for 20 minutes. The reaction was then refluxed for 3 hours. After cooling to room temperature, the mixture was passed through a plug of diatomaceous earth and washed with methanol. After washing off the yellow color in the diatomaceous earth, the diatomaceous earth plug was washed with dichloromethane until the filtrate became colorless. The dichloromethane filtrate was collected and evaporated under reduced pressure. The crude product was purified by a ruthenium dioxide column (prepared by 20% in triethylamine in hexane) eluting with 100% hexanes in hexane to afford 2 g of yellow solid (60% yield) .

Step 4. The product from Step 3 (1.8 g, 2.3 mmol), 2,4-dimethyl-6-m-tolylpyridine (4.5 g, 22.8 mmol), sodium carbonate (1.2 g, 11.4 millimoles) mixed. The system was evacuated and refilled with nitrogen for 3 times. The mixture was heated at 270 ° C (sand bath temperature) for 3 hours. After cooling to room temperature, the mixture was dissolved in dichloromethane and passed through a plug of diatomaceous earth. The diatomaceous earth plug was washed with dichloromethane. The combined fractions were evaporated under reduced pressure. The crude product was purified by EtOAc (EtOAc) eluting eluting The product was further purified by high vacuum sublimation at 240 °C.

Compound 18

Step 1.2-Bromopyridine (8.66 g, 54.8 mmol), 3-methoxyphenylboronic acid (10 g, 65.8 mmol), triphenylphosphine (1.44 g, 5.48 mmol), potassium carbonate ( A mixture of 18.9 grams, 137 millimoles in 100 milliliters of dimethoxyethane and 66 milliliters of water was purged with nitrogen for 20 minutes. Palladium acetate (0.61 g, 2.74 mmol) was then added. The reaction mixture was heated to reflux under nitrogen overnight. The reaction mixture was cooled and water and ethyl acetate were added. The layers were separated and the aqueous layer was extracted with EtOAc. The organic extract was dried over magnesium sulfate, filtered and evaporated to give a crystal. The residue was purified by column chromatography using 0 to 20% ethyl acetate / hexanes. 9.7 g of a clear oil (96% yield) were obtained.

Step 2. A mixture of 2-(3-methoxyphenyl)pyridine (9.7 g, 52.37 mmol) and pyridine hydrochloride (72.6 g, 628.44 m.m.). Water was added to the cooled mixture and then extracted twice with dichloromethane. The organic extract is dried over magnesium sulfate, filtered and evaporated to give The residue. The residue was purified by column chromatography eluting with EtOAc (EtOAc) elute 5 g of a white solid were obtained (56% yield).

Step 3. Preparation of a solution of 3-(pyridin-2-yl)phenol (5 g, 29.21 mmol) in 100 mL dichloromethane. To this solution was added pyridine (4.7 mL, 58.42 mmol) and the solution was cooled in an ice-salt bath. A solution of trifluoromethanesulfonic anhydride (9.8 ml, 58.42 mmol) in 20 ml of dichloromethane was added dropwise to this solution. The reaction was slowly heated and completed after 2 hours. Water and dichloromethane were added and the layers were separated. The aqueous layer was extracted with dichloromethane. The organic extract was dried over magnesium sulfate, filtered and evaporated to give a crystal. The residue was purified by column chromatography using 5, 10, and 15% ethyl acetate / hexanes. 8 g of clear liquid (90% yield) was obtained.

Step 4. 10.7 g (58.5 mmol) of 2-phenyl-4,6-lutidine, 5.4 g (14.6 mmol) of ruthenium chloride, 150 ml of 2-ethoxyethanol and 50 ml of water Mix in a 500 ml 3-neck flask. The system was purged with nitrogen for 15 minutes and then refluxed overnight. After the reaction was cooled to room temperature, the solvent was evaporated under reduced pressure. The residue was washed with methanol to give a white solid (4.1%).

Step 5. Dissolve 3.0 grams of dimer (2.5 millimolar) in 200 milliliters of dichloromethane and add 1.32 grams (5.1 millimoles) of AgOTf and 10 milliliters of methanol. The reaction mixture was stirred at room temperature for 30 minutes. The residue was filtered and washed with EtOAc EtOAc. The filtrate was evaporated to give a yellow solid which was used in the next step without any purification.

Step 6. The product from Step 5 was added along with 3.1 g (10.0 mmol) of product from Step 3 and 150 mL of 2-methoxyethanol. The reaction mixture was heated at 90 °C for 18 hours. The reaction mixture was cooled and purified by using a ceria gel column using 40% dichloromethane in hexanes as a solvent. 1.6 g of a yellow solid were obtained.

Step 9. 1.6 g (1.86 mmol) of step 6 product, 0.86 g (7.0 mmol) of phenylboronic acid, 35 mg (0.037 mmol) of Pd ₂ (dba) ₃ , 62 mg (0.149 mmol) 2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 1.3 g (5.6 mmol) of tripotassium phosphate monohydrate and 150 ml of anhydrous toluene were packed in a 3-necked flask. Nitrogen gas was purged through the reaction mixture for 40 minutes and then heated to reflux overnight. The organic extract was purified by using a ceria gel column using 30% dichloromethane in hexane as the eluent. 1.3 g (about 90% yield) of product was obtained.

Compound 19

Step 1. 25 g (98 mmol) of 3,5-dibromomethylbenzene, 12.2 g (98 mmol) of phenylboronic acid, 3.4 g (2.9 mmol) of Pd(PPh ₃ ) ₄ , 41 Grams (297 mmol) K ₂ CO ₃ , 150 mL DME and 150 mL water were filled in a 500 mL flask. The reaction mixture was heated to reflux under nitrogen overnight. The organic extract was purified by a cerium oxide gel column. 16 g (66% yield) of product was obtained.

Step 2. 10.2 g (41.4 mmol) of step 1 product, 100 ml (50 mmol) of 0.5 M pyridine zinc bromide in THF and 1.5 g (1.29 mmol) Pd (PPh ₃ ) under nitrogen. ₄ ) Add to a dry 200 ml flask. The reaction was refluxed under nitrogen for 5 hours and the organic extract was purified from EtOAc (EtOAc): 8.5 g (85% yield) of product was obtained.

Step 3. 5.2 g (21.2 mmol) of the product of Step 2, 2 g (4.24 mmol) of Ir(acac) _{3 were} placed in a Schlenk tube and heated at 280 ° C for 48 hours under nitrogen. The reaction residue was purified by a cerium oxide gel column. 0.3 g (7.6% yield) of product was obtained.

Compound 20

Step 1. 2-Bromopyridine (40 g, 253 mmol), 3-bromophenylboronic acid (61.0 g, 303.8 mmol), triphenylphosphine (6.64 g, 25.3 mmol), potassium carbonate A mixture of (87.4 g, 632.5 mmol) in 300 ml of dimethoxyethane and 200 ml of water was purged with nitrogen for 20 min. Palladium acetate (2.84 g, 12.65 mmol) was then added. The reaction mixture was heated to reflux under nitrogen. The reaction mixture was cooled and water and ethyl acetate were added. The layers were separated and the aqueous layer was extracted with EtOAc. The organic extract was dried over magnesium sulfate, filtered and evaporated to give a brown oil. Chromatography was purified by elution with 0 to 40% ethyl acetate / hexanes then distilled in vacuo. 45.1 g (52% yield) of product was obtained.

Step 2. 2.5 g (10.7 mmol) of step 1 product, 2.5 g (8.0 mmol) of 3,5-diisopropylphenylboronic acid, 0.3 g (0.259 mmol) Pd(PPh ₃ ) ₄ 3.6 g (26 mmol) of K ₂ CO ₃ , 50 ml of DME and 50 ml of water were placed in a 200 ml flask. The reaction mixture was heated to reflux under nitrogen overnight. The organic extract was purified by a cerium oxide gel column. 1.4 g (56% yield) of product was obtained.

Step 3. 1.3 g (4.1 mmol) of the product from Step 2, 0.58 g (1.17 mmol) of Ir(acac) ₃ and 20 mL of ethylene glycol were added to a 100 mL flask and heated to reflux overnight. The organic extract was purified by a cerium oxide gel column. 0.7 g (56% yield) of product was obtained.

Compound 21

Step 1. 2.5 g (10.7 mmol) of 2-(3-bromophenyl)pyridine, 2.4 g (16 mmol) of 3,5-dimethylphenylboronic acid, 0.37 g (0.321 mmol) Pd(PPh ₃ ) ₄ , 4.5 g (32.6 mmol) K ₂ CO ₃ , 50 ml DME and 50 ml water were filled in a 200 ml flask. The reaction mixture was heated to reflux under nitrogen overnight. The organic extract was purified by a cerium oxide gel column. 2.3 g (83% yield) of product was obtained.

Step 2. 2.0 g (7.68 mmol) of the product of Step 1, 1.1 g (2.14 mmol) of Ir(acac) ₃ and 20 mL of ethylene glycol were added to a 100 ml flask and heated to reflux overnight. The organic extract was purified by a cerium oxide gel column. 1.7 g (86% yield) of product was obtained.

Compound 22

Step 1. 3.5 g (15.0 mmol) of 2-(3-bromophenyl)pyridine, 3.5 g (19.7 mmol) of 3,5-diethylphenylboronic acid, 0.4 g (0.345 mmol) Pd(PPh ₃ ) ₄ , 6.2 g (44.9 mmol) K ₂ CO ₃ , 100 ml DME and 100 ml water were filled in a 250 ml flask. The reaction mixture was heated to reflux under nitrogen overnight. The organic extract was purified by a cerium oxide gel column. 3.2 g (74% yield) of product was obtained.

Step 2. 2.2 g (7.64 mmol) of the product from Step 1, 1.04 g (2.12 mmol) of Ir(acac) ₃ and 30 ml of ethylene glycol were added to a 100 ml flask and heated to reflux overnight. The organic extract was purified by a cerium oxide gel column. 1.5 g (67% yield) of product was obtained.

Compound 23

Step 1. 2-(3-Bromophenyl)pyridine (15 g, 64 mmol), 3-biphenylboronic acid (13.70 g, 69 mmol), potassium carbonate (27 g, 195 mmol) A mixture of 100 ml of dimethoxyethane and 60 ml of water was purged with nitrogen for 20 minutes. Was then added Pd (PPh _{3) 4} (2.3 g, 2 mmol) and the reaction mixture was heated at reflux overnight under nitrogen. The second angel reaction mixture was cooled and diluted with water and ethyl acetate. The layers were separated and the aqueous layer was extracted with EtOAc. The organic layer was dried over MgSO4, filtered and evaporated The oil was purified by column chromatography eluting with 5 to 30% ethyl acetate /hexane to afford 19 g of crude oil as product.

Step 2. 1.5 g (4.8 mmol) of step 1 ligand, 0.68 g (1.39 mmol) of Ir(acac) ₃ and 25 ml of ethylene glycol were placed in a 100 ml flask. The reaction mixture was heated to reflux under nitrogen overnight. The reaction was cooled and filtered and washed with EtOAc (3×50 mL). The solid was purified by a cerium oxide gel column to give 0.8 g (yield: 51%).

Compound 24

Step 1. 2-(3-Bromophenyl)pyridine (12.2 g, 52.10 mmol), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaboron -2-yl)phenol (13.76 g, 62.53 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (856 mg, 2.08 mmol), tripotassium phosphate A mixture of hydrate (36 g, 156.3 mmol) in 180 ml of dioxane and 18 ml of water was purged with nitrogen for 20 min. Then Pd ₂ (dba) ₃ (477 mg, 0.52 mmol) was added. The reaction mixture was heated at 100 ° C for 3 h under nitrogen then cooled to room temperature overnight. Water was added to the reaction mixture and the mixture was extracted three times with ethyl acetate. The organic extract was dried over magnesium sulfate, filtered and evaporated to give a crystal. The residue was purified by column chromatography eluting with 20% 40%EtOAcEtOAc

Step 2. A mixture of 12.5 g (50.6 mmol) of Step 1 product, 12 mL of pyridine and 200 mL of dichloromethane in a 500 mL round bottom flask at 0 °C. 14.3 g (101.2 mmol) of trifluoromethanesulfonic anhydride was added. The mixture was stirred at 0 ° C for 30 minutes and at room temperature for 1 hour. The reaction mixture was washed several times with water. After evaporation of the solvent, 19.0 g (about 100% yield) of product was obtained.

Step 3. 8.8 g (23.2 mmol) of product from step 2, 4.7 g (46 mmol) of isobutylboronic acid, 0.02 g of Pd ₂ (dba) ₃ (0.23 mmol), 0.4 g (0.965) Millol) 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 16.7 g (72.6 mmol) K ₃ PO ₄ .H ₂ O and 300 ml of toluene filled in 500 ml round In the bottom flask. The reaction mixture was heated to reflux under nitrogen overnight while stirring. The reaction mixture was purified by cerium oxide gel chromatography using 10% ethyl acetate in hexane as a solvent. 5.8 g (yield 87%) of product was obtained.

Step 4. 2.0 g (6.9 mmol) of the ligand from Step 3, 0.97 g (2.0 mmol) of Ir(acac) ₃ and 25 mL of ethylene glycol were packed in a 100 mL round bottom flask. The reaction mixture was heated to reflux under nitrogen overnight. The reaction mixture was cooled and 100 mL of methanol was added. The solid was filtered, washed with methanol and dried. After purification of the ruthenium dioxide column, 1.3 g (62% yield) of product was obtained.

Compound 25

2.0 g (2.55 mmol) of Ir(ppy) ₃ borate (prepared according to USPTO No. 11/951,879), 1.6 g (7.6 mmol) of 4-isobutylbromobenzene, 0.21 g (0.52 m) Mole) 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 1.1 g (5.1 mmol) potassium phosphate, 80 ml of toluene and 8 ml of water were mixed in a 3-necked flask. The mixture was purged with nitrogen for 30 minutes. To the degassed mixture was added 0.12 g (0.127 mmol) of Pd ₂ (dba) ₃ . The reaction was refluxed overnight under a nitrogen atmosphere. After cooling to room temperature, the reaction mixture was filtered through a pad of Celite. The yellow precipitate on the celite bed was washed with dichloromethane. The solution was dried over magnesium sulfate. After evaporation of the solvent, the residue was purified by using 1:1 hexanes and dichloromethane as solvent. 1.65 g of product was obtained.

Compound 26

2.0 g (2.55 mmol) of Ir(ppy) ₃ borate, 1.35 g (7.69 mmol) of 4-methylbromobenzene, 0.21 g (0.52 mmol) of 2-dicyclohexylphosphino-2 '6'-Dimethoxybiphenyl, 1.6 g (7.5 mmol) of potassium phosphate, 80 ml of toluene and 8 ml of water were mixed in a 3-necked flask. The mixture was purged with nitrogen for 30 minutes. To the degassed mixture was added 0.12 g (0.127 mmol) of Pd ₂ (dba) ₃ . The reaction was refluxed overnight under a nitrogen atmosphere. After cooling to room temperature, the reaction mixture was filtered through a pad of Celite. The yellow precipitate on the celite bed was washed with dichloromethane. The solution was dried over magnesium sulfate. After evaporation of the solvent, the residue was purified by using 1:1 hexanes and dichloromethane as solvent. 1.55 g (83% yield) of product was obtained.

Compound 27

Step 1. Fill 10.0 g (49.2 mmol) of 4-bromophenylethanol, 9.17 g (54.1 mmol) of DAST with 150 ml of anhydrous dichloromethane in a dry 250 ml flask and mix the reaction under nitrogen. Stir at room temperature for 20 hours. A NaHCO ₃ solution (40 g in 300 mL water) was slowly added to quench the reaction. After the addition, it was stirred for another 2 hours until no CO ₂ escaped. The organic extract was purified by a silica gel column to afford 9 g (yield: 91%).

Step 2. 2.0 g (2.55 mmol) of Ir(ppy) ₃ borate, 1.0 g (5.0 mmol) of step 1 product, 0.21 g (0.52 mmol) of 2-dicyclohexylphosphino-2 '6'-Dimethoxybiphenyl, 1.6 g (7.5 mmol) of potassium phosphate, 80 ml of toluene and 8 ml of water were mixed in a 3-necked flask. The mixture was purged with nitrogen for 30 minutes. To the degassed mixture was added 0.12 g (0.127 mmol) of Pd ₂ (dba) ₃ . The reaction was refluxed overnight under a nitrogen atmosphere. After cooling to room temperature, the reaction mixture was filtered through a pad of Celite. The yellow precipitate on the celite bed was washed with dichloromethane. The solution was dried over magnesium sulfate. After evaporation of the solvent, the residue was purified using 1:1 hexanes and methylene chloride as a solvent to afford 1.65 g (85% yield) product.

Compound 28

Step 1. Slowly add 9.5 ml of BuLi (23.75 mmol; 2.5 M BuLi in hexane) to 4.0 g (19.7 mmol) in 100 ml of anhydrous THF at -78 °C. Fluoroethyl) bromobenzene. The mixture was stirred at -78 ℃ 1 hour and then at -78 ℃ 2.6 ml (23.7 mmol) in 10 ml of anhydrous THF of B (OMe) _3. The reaction was allowed to warm to rt and stirred overnight. 60 ml of HCl (1 M) was added and the mixture was stirred for 3 hours. Ethyl acetate was added to the reaction solution to extract an organic phase. The organic phases were combined and evaporated. A white solid was obtained which was washed with hexanes and dried. The resulting boric acid was used in the next step without further purification.

Step 2. 2.5 g (14.8 mmol) of boric acid from step 1, 3.0 g (13.5 mmol) of 2-(3-bromophenyl)pyridine, 0.48 g (0.415 mmol) Pd (PPh ₃ ) ₄ , 5.6 g (40.57 mmol) K ₂ CO ₃ , 50 ml DME and 50 ml water were added to a 200 ml flask. The reaction mixture was heated to reflux under nitrogen overnight. The organic extract was purified by a cerium oxide gel column. 3.2 g (86% yield) of product was obtained.

Step 3. 3.0 g (10.8 mmol) of the ligand of step 2, 1.3 g (2.7 mmol) of Ir(acac) ₃ and 50 ml of ethylene glycol were added to a 100 ml flask and heated to reflux under nitrogen. overnight. The organic extract was purified by a cerium oxide gel column. 1.65 g (60% yield) of product was obtained.

Compound 29

Step 1. Carbazole (10 g, 60 mmol), 1-bromo-2-methylpropane (16.4 g, 120 mmol), KOH (8.4 g, 150 mmol), 18-crown- Mix 6 (160 mg, 0.6 mmol) and 50 ml of DMF and stir at room temperature for 2 days. The mixture was diluted with 400 ml of water and extracted three times with dichloromethane. The combined organic layers were dried over MgSO ₄ Gan sulfate and evaporated under reduced pressure. By silicon dioxide column using hexane up to 5% in CH ₂ Cl ₂ to the crude product was purified to provide 12 g of product (66% yield).

Step 2. Mix 9-isobutyl-9H-carbazole (12 g, 53.7 mmol), N-bromosuccinimide (9.6 g, 53.7 mmol) and 300 mL DMF at room temperature Stir for 2 days. The solvent was evaporated under reduced pressure. The mixture was redissolved in dichloromethane and washed with water. The organic layer was collected and washed with dry Gan MgSO _4, to provide 16.7 g of product (100% yield).

Step 3. 3-Bromo-9-isobutyl-9H-carbazole (16.7 g, 55 mmol), pentamidine diboron (28 g, 110 mmol), potassium acetate (16 g, 165 m) Mol) was mixed with 400 ml of anhydrous dioxane and purged with nitrogen for 20 minutes. Then Pd(dppf) ₂ Cl _{2 was} added and the system was purged again with nitrogen for 15 minutes. After heating at 90 ° C overnight, the solvent was evaporated. The crude product was purified by a ruthenium dioxide column using up to 10% ethyl acetate in hexane to afford 3 g of purified product (16% yield).

Step 4. 9-Isobutyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaboron -2-yl)-9H-carbazole (3.1 g, 8.9 mmol), bromopyridine (2.8 g, 17.8 mmol), potassium carbonate (3.7 g, 26.6 mmol), triphenylphosphine (0.28) Grams, 1.1 mmol, 60 ml of dimethoxyethane and 20 ml of water were mixed in a 3-neck flask. The system was purged with nitrogen for 30 minutes. Palladium acetate (60 mg, 0.27 mmol) was then added and the mixture was purged with nitrogen for a further 15 min. After refluxing overnight, the organic layer was collected and evaporated. The mixture was purified by a ruthenium dioxide column using up to 10% ethyl acetate in hexane to afford 2.1 g of white solid (79% yield).

Step 5. Mix 3-phenyl-9-isobutyl-9H-carbazole (2.1 g, 7 mmol), Ir(acac) ₃ (0.86 g, 1.7 mmol) and 20 mL of ethylene glycol. . The mixture was evacuated and refilled with nitrogen, 3 times, and then heated at 220 ° C for 2 days. After the mixture was cooled to room temperature, methanol was added to precipitate a complex. The residue was collected and washed with methanol. Purification of the crude product and 1 CH ₂ Cl ₂ in hexanes to give 1.2 g as a yellow solid (65% yield): silicon dioxide by using a column. The product was further purified by high vacuum sublimation at 290 °C.

Compound 30

Step 1. 5.3 g (30 mmol) of 2,6-diisopropylaniline, 9.36 g (30 mmol) of 2,2'-dibromobiphenyl, 0.99 g (2.4 mmol) 2- Dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 8.8 g (90 mmol) sodium tributoxide and 0.55 g (0.6 mmol) Pd ₂ (dba) ₃ in 100 ml Mix in xylene. The mixture was refluxed under nitrogen overnight. After cooling to room temperature, the reaction mixture was filtered through a pad of Celite. The product was subjected to column chromatography using hexane. After the column was obtained 5.8 g of product (59% yield).

Step 2. 5.7 g (17 mmol) of 9-(2,6-diisopropylphenyl)-9H-indazole was dissolved in 100 mL of DMF. To this solution was added 3.1 g (17 mmol) of NBS in small portions. The reaction was allowed to react for 2 hours. Water is added to precipitate the product. The product was dissolved in dichloromethane, washed with water and dried over magnesium sulfate. After evaporation of the solvent, 6.78 g of product was obtained which contained about 72% product according to HPLC. The product was used in the next step without further purification.

Step 3. 6.78 g of 3-bromo-9-(2,6-diisopropylphenyl)-9H-carbazole, 5.8 g (23 mmol) of pentamidine diboron, 4.9 g (50 mmol) Potassium acetate, 100 ml of DMSO were mixed in a 3-necked flask. The system was purged with nitrogen for 30 minutes. 0.4 g (0.5 mmol) of Pd(dppf) ₂ Cl ₂ was added to the mixture. The reaction was heated at 80 ° C for 15 hours. The reaction was monitored by TLC. After the reaction was completed, the product was precipitated using 300 ml of water. The solid was subjected to column chromatography using 1:5 dichloromethane and hexane. 4.3 g of product were obtained (57% yield).

4.3 g (9.5 mmol) of borate, 1.8 g (11.4 mmol) of 2-bromopyridine, 6.4 g (28.5 mmol) of potassium phosphate, 0.16 g (0.38 mmol) of 2-dicyclohexyl Phosphyl-2',6'-dimethoxybiphenyl, 100 ml of toluene and 10 ml of water were mixed in a 3-necked flask. The system was purged with nitrogen for 30 minutes. 0.09 g (0.09 mmol) of Pd ₂ (dba) _{3 was} added and the mixture was heated to reflux overnight. The product was subjected to column chromatography using 5% ethyl acetate in hexane. 1.0 g of product was obtained after the column.

0.9 g (2.2 mmol) of 9-(2,6-diisopropylphenyl)-3-(pyridin-2-yl)-9H-indazole and 0.22 g (0.45 mmol) of Ir (acac) ₃ ) Heated in 20 ml of ethylene glycol for 48 hours. After cooling to room temperature, 100 ml of methanol was added. The precipitate was collected by filtration. The solid was purified by column using 1:1 dichloromethane and hexane as a solvent. After purification of the column, 0.07 g of product was obtained. The product was further purified by high vacuum sublimation at 350 °C.

Compound 31

Step 1. 4.5 g (21.9 mmol) of 5-bromo-2-fluoro-m-xylene, 6.2 g (24.1 mmol) of pinacol diborane, 0.54 g (0.66 mmol) of Pd (dppf) ₂ Cl ₂ .CH ₂ Cl ₂ , 6.4 g (65.7 mmol) of KOAc and 100 ml of DMSO were filled in a 200 ml flask. The reaction mixture was heated at 80 ° C under nitrogen overnight. The organic extract was purified by using a ceria gel column using 10% ethyl acetate in hexane as the eluent. 4.3 g (79.6% yield) of product was obtained.

Step 2. 4.0 g (16 mmol) of step 1 product, 2.3 g (14.5 mM) bromopyridine, 0.51 g (0.44 mmol) Pd(PPh ₃ ) ₄ and 6 g (43.3 mmol) K ₂ CO ₃ , 50 ml of DME and 50 ml of water were added to a 250 ml flask. The reaction was refluxed under nitrogen for 5 hours. The reaction was then treated with a cerium oxide gel column using 4% ethyl acetate in hexane as the eluent. 2.8 g (96% yield) of product was obtained.

Step 3. 2.1 g (10.2 mmol) of Step 2 product and 1.27 g (2.6 mmol) of Ir(acac) _{3 were} added to a Schlenk tube and heated at 245 ° C for 28 hours under nitrogen. The precipitate was collected and purified by using a cerium oxide gel column using 25% dichloromethane in hexane as the eluent. 0.25 g (11% yield) of product was obtained.

Compound 32

Step 1. 12.6 g (80 mmol) of 2-bromopyridine, 12 g (80 mmol) of 3,5-phenylboronic acid, 0.18 g (0.8 mmol) of palladium acetate, 0.84 g (3.2 mmol) The ear) triphenylphosphine and 33 g (240 mmol) of potassium carbonate, 80 ml of dimethoxyethane and 50 ml of water were purged with nitrogen and heated to reflux for 12 hours. After cooling, the organic layer was separated, washed with water, and dried over MgSO ₄ Gan dry. The product was isolated by column chromatography using 5% ethyl acetate in hexanes as a solvent.

Step 2. A mixture of 1 g (5.45 mmol) of 2-(3,5-dimethylphenyl)pyridine and 0.53 g (1.09 mmol) of Ir(acac) ₃ was heated to an external temperature using a sand bath. Hold at 290 ° C for 3 hours. The mixture was cooled and dissolved in dichloromethane. The product was packed on celite and separated by column chromatography using hexane/dichloromethane as a solvent (40% dichloromethane). 0.1 g of product was collected.

Alternative method for compound 32

Step 1. 6.6 g (36 mmol) of 2-(3,5-dimethylphenyl)pyridine and 4.23 g (12 mmol) of ruthenium chloride, 90 ml of 2-ethoxyethanol and 30 ml The water was mixed and heated to reflux under nitrogen overnight. After cooling to room temperature, the solid was collected by filtration and washed thoroughly with methanol and hexane. The solid was dried and used in the next step without further purification. 6 g of the desired product were obtained (84% yield).

Step 2. 6.0 g (5 mmol) of the dimer, 9.2 g (50 mmol) of 2,2,6,6-tetramethylheptane-3,5-dione, 2.7 g (25 Millol) sodium carbonate and 100 ml of 2-ethoxyethanol were mixed in a flask and heated under reflux for 4 hours under nitrogen. After cooling to room temperature, the mixture was filtered through a bed of diatomaceous earth. The solid was washed thoroughly with methanol. The solid at the top of the diatomaceous earth bed was dissolved in dichloromethane. The solution was then passed through a triethylamine treated cerium oxide gel plug. After evaporation of the solvent, 5.9 g of desired product (yield: 80%) was obtained.

Step 3. 2.95 g (4 mmol) of ^t Buacac complex, 7.3 g (40 mmol) of 2-(3,5-dimethylphenyl)pyridine, and 2.1 g (20 mmol) Sodium carbonate is mixed and carefully degassed. The mixture was heated at 270 ° C for 24 hours and then at 290 ° C for 6 hours. The reaction was cooled to room temperature. Add 30 ml of dichloromethane. The mixture was filtered through celite. The solvent was evaporated and 300 mL of hexane was added to the residue. The mixture was stirred overnight. The solid was collected by filtration. The unreacted starting material is removed. The solid was further purified by using a ceria gel column using 3:1 hexanes and dichloromethane as solvent. After purification, 0.7 g of material was obtained. The complex was further purified by high vacuum sublimation. 0.4 g of product was obtained.

Compound 33

Step 1. 8.1 g (51.5 mmol) of 2-bromopyridine, 7 g (51.5 mmol) of o-tolylboronic acid, 0.47 g (0.51 mmol) of Pd ₂ (dba) ₃ , 0.84 g (2.06) Mixture of millimolar 2-cyclohexylphosphino-2',6'-dimethoxybiphenyl and 32 g (154.5 mmol) of tripotassium phosphate, 100 ml of toluene and 30 ml of water with nitrogen . The solution was heated to reflux for 12 hours. After cooling, the organic layer was separated and dried over MgSO ₄ . The product was isolated by column chromatography using hexane/ethyl acetate (5% ethyl acetate) as a solvent. The solvent was removed by rotary evaporation and the product was evaporated in vacuo to afford 6 g (35.5 m.

Step 2. A mixture of 1.5 g (8.8 mmol) of 2-(m-tolyl)pyridine and 0.7 g (1.45 mmol) of Ir(acac) ₃ was heated in a sand bath to an external temperature of 290 ° C for 12 hours. . The reaction was cooled and dissolved in dichloromethane. The product was packed on celite and separated by column chromatography using hexane/dichloromethane as a solvent (40% dichloromethane). A 0.75 g (1.07 mmol) product was collected.

Compound 34

Step 1. 3.0 g (12.8 mmol) of 5-bromo-2-phenylpyridine, 2.3 g (15.4 mmol) of 2,6-dimethylphenylboronic acid, 8.6 g (38.4 mmol) of phosphoric acid Potassium, 0.21 g (0.52 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 100 ml of toluene and 10 ml of water were mixed in a 3-necked flask. The system was purged with nitrogen and nitrogen for 30 minutes. 0.12 g (0.13 mmol) of Pd ₂ (dba) _{3 was} added and the mixture was heated to reflux overnight. After cooling to room temperature, the reaction mixture was filtered through a pad of Celite. The product was subjected to column chromatography using 5% ethyl acetate in hexane. After the column, 3.0 g of product (90% yield) was obtained.

3.0 g (11.6 mmol) of 5-(2,6-dimethylphenyl)-2-phenylpyridine and 1.1 g (2.3 mmol) of Ir(acac) ₃ were heated in 30 ml of ethylene glycol. Reflux for 42 hours. After cooling to room temperature, 100 ml of methanol was added. The precipitate was collected by filtration. The solid was purified by using a column of 1:1 dichloromethane and hexane as a solvent. 1.0 g of product was obtained. The product was further purified by high vacuum sublimation at 270 °C.

Synthesis of Compound 35 Compound 35: 0.52 g (0.64 mmol) or more of monoborate, 0.3 g (1.93 mmol) of phenylboronic acid, 0.006 g (0.0064 mmol) of hydrazine (dibenzylideneacetone) Palladium (0) [Pd ₂ (dba) ₃ ], 0.10 g (0.025 mmol) 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl (SPhos) and 0.4 g (1.92 Millol) potassium phosphate (K ₃ PO ₄ ) was weighed into the flask. 30 ml of toluene and 10 ml of water were used as a solvent and the solution was purged with nitrogen. The solution was heated to reflux for 12 hours. After cooling, the organic layer was separated and dried over MgSO ₄ . The product was isolated by column chromatography using hexane/dichloromethane as a solvent. The solvent was removed by rotary evaporation and the product was dried under vacuum. The product was further purified by high vacuum sublimation at 250 ° C to give 0.3 g (0.39 mmol).

Synthesis of Compound 36 Compound 36:

Preparation of 2-bromopyridine (40 g, 253 mmol), 3-bromophenylboronic acid (61.0 g, 303.8 mmol), triphenylphosphine (6.64 g, 25.3 mmol), potassium carbonate (87.4 g) , 632.5 millimoles) a mixture of 300 ml of dimethoxyethane and 200 ml of water. Nitrogen gas was bubbled directly into the mixture for 20 minutes, then palladium acetate (2.84 g, 12.65 mmol) was added. The reaction mixture was heated to reflux under nitrogen. At the end, traces of 2-bromopyridine were detected by TLC. Therefore, an additional 10 grams of 2-bromophenylboronic acid was added and the reaction was allowed to continue to reflux overnight. The reaction mixture was cooled and water and ethyl acetate were added. The layers were separated and the aqueous layer was extracted with EtOAc. The organic layer was dried over MgSO4, filtered and evaporated The oil was purified by column chromatography using 0 to 40% ethyl acetate / hexanes eluting then evaporated in vacuo. 45.1 grams of the desired product (52% yield) was obtained as confirmed by GC-MS.

Preparation of 2-(3-bromophenyl)pyridine (12.2 g, 52.10 mmol), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaboron -2-yl)phenol (13.76 g, 62.53 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (856 mg, 2.08 mmol), tripotassium phosphate A mixture of hydrate (36 g, 156.3 mmol) in 180 ml of dioxane and 18 ml of water. Nitrogen gas was bubbled directly into the mixture for 20 minutes, then hydrazine (dibenzylideneacetone) dipalladium (0) (477 mg, 0.52 mmol) was added. The reaction mixture was heated at 100 ° C for 3 h under nitrogen then cooled to room temperature overnight. Water was added to the reaction mixture and the mixture was extracted three times with ethyl acetate. The organic extract was dried over magnesium sulfate, filtered and evaporated to give a crystal. The residue was purified by column chromatography using 20 to 40% ethyl acetate / hexanes. 12.5 g of a yellow oil (97% yield) was obtained as confirmed by GC-MS.

12.5 g (50.6 mmol) of 3'-(pyridin-2-yl)biphenyl-3-ol, 12 ml of pyridine, and about 200 ml of dichloromethane were mixed in a 500 ml round bottom flask at 0 °C. To the mixture, 14.3 g (101.2 mmol) of trifluoroacetic anhydride was added and stirred at 0 ° C for 30 minutes, and then stirred at room temperature for 1 hour. The reaction mixture was washed several times with water. Approximately 19 grams (about 100% yield) of the triflate was obtained after evaporation of the solvent as confirmed by GC-MS.

8.8 g (23.2 mmol) of 3'-(pyridin-2-yl)biphenyl-3-yl trifluoromethanesulfonate, 4.7 g (46 mmol) of isobutane boronic acid, 211 mg of Pd ₂ ( Dba) ₃ (0.23 mmol), 396 mg (0.965 mmol) S-Phos, 16.7 g (72.6 mmol) K ₃ PO ₄ H ₂ O, and 300 mL of toluene in a 500 mL round bottom flask . The reaction mixture was heated up to reflux overnight under nitrogen while stirring. The reaction mixture was purified by cerium oxide gel chromatography using 10% (v/v) of ethyl acetate in hexane as a solvent. Approximately 5.8 grams of solid (yield 87%) product was obtained as confirmed by GC-MS.

3.4 g (11.8 mmol) of 2-(3'-isobutylbiphenyl-3-yl)pyridine, 2.0 g (5.3 mmol) of IrCl ₃ .3H ₂ O, and 150 ml of solvent mixture (2 B Oxyethanol/water: 3:1) was filled in a 250 ml round bottom flask. The reaction mixture was heated up to reflux overnight under nitrogen. The reaction mixture was allowed to cool and about 100 mL of methanol was added and then filtered. The solid was washed with methanol and dried. Approximately 3.85 g of the chloro-bridged oxime dimer was obtained and used in the next step without further purification.

Preparation of 2-bromopyridine (8.66 g, 54.8 mmol), 3-methoxyphenylboronic acid a mixture of (10 g, 65.8 mmol), triphenylphosphine (1.44 g, 5.48 mmol), potassium carbonate (18.9 g, 137 mmol) in 100 ml of dimethoxyethane and 66 ml of water . Nitrogen gas was bubbled directly into the mixture for 20 minutes, then palladium acetate (0.61 g, 2.74 mmol) was added. The reaction mixture was heated to reflux under nitrogen overnight. The reaction mixture was cooled and water and ethyl acetate were added. The layers were separated and the aqueous layer was extracted with EtOAc. The organic layer was dried over magnesium sulfate, filtered and evaporated to yield The residue was purified by column chromatography using 0 to 20% ethyl acetate / hexanes. 9.7 g of a clear oil (96% yield) was obtained as confirmed by GC-MS.

A mixture of 2-(3-methoxyphenyl)pyridine (9.7 g, 52.37 mmol) and pyridine hydrochloride (72.6 g, 628.44 mmol) was prepared. The mixture was heated to 220 °C. The reaction was allowed to proceed for 2 hours. Water was added to the cooled mixture and then extracted twice with dichloromethane. The organic extract was dried over magnesium sulfate, filtered and evaporated to give a crystal. The residue was purified by column chromatography using EtOAc EtOAc (EtOAc) elute 5 g of a white solid (56% yield) were obtained as confirmed by GC-MS.

Preparation of 3-(pyridin-2-yl)phenol (5 g, 29.21 mmol) in 100 ml two a solution in methyl chloride. To this solution was added pyridine (4.7 mL, 58.42 mmol) and the solution was cooled in an ice-salt bath. A solution of trifluoromethanesulfonic anhydride (9.8 ml, 58.42 mmol) in 20 ml of dichloromethane was added dropwise to this solution. The reaction was allowed to warm slowly and was completed after 2 hours. Water and dichloromethane were added and the layers were separated. The aqueous layer was extracted with dichloromethane. The organic layer was dried over magnesium sulfate, filtered and evaporated to yield The residue was purified by column chromatography using 5, 10 and 15% ethyl acetate / hexanes. 8 g of clear liquid (90% yield) was obtained as confirmed by GC-MS.

3.85 g (2.41 mmol) of the above-mentioned chlorine bridged ruthenium dimer, 1.42 g (5.3 mmol) of silver trifluoromethanesulfonate AgOSOCF ₃ , 2.93 g (9.64 mmol) of trifluoromethanesulfonate 3-( Pyridin-2-yl)phenyl ester and about 300 ml of 2-ethoxyethanol were mixed in a 500 ml round bottom flask. The mixture was heated to reflux for a maximum of 24 hours under nitrogen. The reaction mixture was purified on a cerium oxide gel using 50% dichloromethane in hexanes. About 900 mg of product was isolated from the reaction mixture, which contained a tetradentate heteromixed complex. The product was confirmed by LC-MS. The desired portion can be obtained by column chromatography.

700 mg (0.647 mmol) of triflate ruthenium complex, 394 mg (3.23 mmol) of phenylboronic acid, 60 mg of Pd ₂ (dba) ₃ (0.065 mmol), 110 mg ( 0.268 mmoles of S-Phos, 840 mg (3.65 mmol) of K ₃ PO ₄ .H ₂ O and 50 ml of anhydrous toluene were placed in a 100 ml three-necked flask. The reaction mixture was bubbled with nitrogen for 30 minutes and then heated to reflux for a maximum of 20 hours under nitrogen. The reaction mixture was separated on a ceria gel column. 610 mg solid (99% yield) was obtained as confirmed by NMR and LC-MS.

All devices are made by high vacuum (<10 ^-7 Torr) thermal evaporation. The anode electrode is about 1200 angstroms of indium tin oxide (ITO). The cathode system consisted of 10 angstroms of LiF followed by 1,000 angstroms of Al. Immediately after fabrication, all devices were encapsulated in an epoxy sealed glass cover in a nitrogen glove box (<1 ppm H ₂ O and O ₂ ) and a moisture absorbent was incorporated into the package.

All device examples have an organic stack consisting of: 100 angstrom thick copper phthalocyanine (CuPc) or compound A as a hole injection layer (HIL), 300 angstroms 4, 4'- starting from the ITO surface. Bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD) as a hole transport layer (HTL), 300 Å doped with 6-10 wt% dopant emitter ( The compound of the present invention and the comparative compound) 4,4'-bis(N-carbazolyl)biphenyl (CBP), compound G or compound H are used as an emissive layer (EML). The electron transport layer (ETL) is composed of 50 angstroms as the HTP of ETL2 and 450 angstroms as the bismuth (8-hydroxyquinolinyl) aluminum (Alq ₃ ) of ETL1, or 100 angstroms as the compound H of ETL2 and 400 angstroms as the Alq of ETL1. ₃ composition. Current-voltage-luminance (IVL) characteristics, electroluminescence properties [Emission Max (Em _max ), full width at half maximum (FWHM) and CIE coordinates] and operating lifetime were measured and summarized in Table 1 below. A typical display brightness level of 1000 cd/m ^{2 is} selected for the green lighting device for comparison between different devices. For device operational stability, all device examples and comparative device examples were tested at a constant current density (J) of 40 mA/cm ² and room temperature. The initial brightness (L ₀ ) at room temperature at J = 40 mA/cm ² is provided in Table 1 below.

The present invention provides a specific device in which Compound 11 or Compound 35 is the emissive dopant and Compound H or Compound G is the host material.

As used herein, the following compounds have the following structure:

Specific emissive dopants for the OLED emissive layer are also provided, which results in devices having particularly good performance. Specifically, a device using the compound 25 or 26 as an emission dopant in the emission layer is shown in Table 1 below. The device stability using devices 25 and 26 as emitters, respectively, demonstrates improved device stability, which indicates that alkylphenyl substitution can be beneficial. Abbreviation for Cmpd.

Alkyl substitution on the 5'-phenyl group can be used to shift the evaporation temperature and stability, narrow the emission, and increase device efficiency. The heterodyne nature of only 25 and 26 with one of the substituted 2-phenylpyridines keeps the evaporation temperature low (as shown in Table 1), which is important for OLED manufacturing because of the need to make such materials The heating is extended and the low evaporation temperature is transferred to less thermal stress, which usually results in a more complete evaporation. Alkyl substitution on the 5'-phenyl group also increases solubility (as shown in Table 1), which is critical in the fabrication of devices based on solution methods (e.g., ink jet printing). The 5' alkylphenyl group also narrows the emission and is preferred for use in OLEDs for display applications because more saturated colors can be achieved. Furthermore, the use of the devices of compounds 25 and 26 demonstrates that the use of heteroconjugates can impart high device efficiencies.

Likewise, devices having an emissive layer using heterocompatible compounds 6, 35, 11, 18 or 2 as dopants can result in devices having particularly good properties. In particular, the device uses Compound 6 as the emissive layer of the dopant, the emissive layer with Compound 35 as the dopant, the emissive layer with Compound 35 as the dopant and Compound H as the host material, with Compound 11 as the doping And the compound H serves as an emissive layer of the host material, an emissive layer using the compound 18 as a dopant, and/or an emissive layer using the compound 2 as a dopant. Such devices often have one or more improvements in device stability, line width, or device efficiency, as shown in Table 1.

The present invention provides a particular Ir(6-alkyl ppy) type of compound which results in a device having a particularly narrow linewidth of light. In particular, the device used a hetero-compound compound 35 or 11 as an emissive dopant as shown in Table 1. Substitution at the 6 position is believed to have this effect because it contributes to the spatial effect of the Ir complex, resulting in a relatively long N-Ir bond that is transferred to a narrower emission. Thus, the Ir(ppy) compound has a 6-alkyl group and is particularly useful for achieving narrow ray linewidths and improved device stability with heterogeneous properties without significantly increasing the evaporation temperature compared to the homogeneous counterpart.

Table 1 is a summary of device data. Comparative Example 1 and Apparatus Example 1-2 had the same device structure except that Comparative Example 1 used Ir(ppy) ₃ as an emitter, and Device Examples 1-3 used Compounds 25 and 26 as emitters, respectively. Compound 25 has an isobutylphenyl group at the 5' position and a compound 26 has a methylphenyl group at the 5' position. Comparative Example 1 and Apparatus Example 1-2 have T _{80% of} 59, 83, and 90 hours, _respectively (which is defined as the time taken for the initial brightness L _{0 to} fall to 80% of its initial brightness). This result indicates that alkylphenyl substitution can contribute to device stability as assumed in U.S. Patent No. 2,050,119, 485 A1. However, the heterogeneous nature of compounds 25 and 26 having only one of the substituted 2-phenylpyridines kept the evaporation temperature low, only a few ° C higher than Ir(ppy) ₃ . Low evaporation temperatures are important for OLED fabrication because of the need to extend the heating of the materials, and the low evaporation temperature is transferred to less thermal stress, which typically results in more complete evaporation. The alkyl substitution on the 5'-phenyl group can be further used to convert the evaporation temperature and solubility. In the fabrication of devices based on solution methods (such as inkjet printing), it is critical to have high solubility. The results also show that the 5'-alkylphenyl group also narrows the emission. Comparative Example 1 had a FWHM of 74 nm, while Device Examples 1 and 2 had FWHMs of 68 and 70 nm, respectively. Since more saturated colors can be achieved, narrow emission is preferred for OLEDs for display applications. Further, Comparative Example 1 and Apparatus Examples 1 and 2 had device efficiencies of 50, 56, and 59 cd/A at 1000 cd/m ² , respectively. This indicates that the use of heteroconjugates can give high device efficiency.

A comparison of more homogeneous and hetero-matching based on structurally similar ligands can be found in Table 1. Comparative Example 2 (with homogeneous compound B) and device example 4 (with heterocompatible compound 3) had T _{80% of} 63 and 47 hours, _respectively . The FWHM is 74 nm and the device efficiency is about 60 cd/A. In this case, the heterogeneous nature does not provide a benefit. Comparative Example 3 (with homogenous compound C, disclosed in WO06014599A2) and device example 5 (with heterocompatible compound 6) have T _{80% for} 12 and 46 hours, _respectively . The FWHM is 72 nm and the device efficiencies are 41 and 59 cd/A, respectively. In this case, the heterogeneous nature provides benefits to device stability and efficiency. Comparative Example 4 (with homogeneous compound D, disclosed in WO06014599A2), device example 6 (with heterogeneous compound 35), device example 7 (with heterocompatible compound 35 and compound H as host material), and device example 8 (with different Formulation 11 and Compound H as host materials have T _{80% of} 14, 18, 85 and 38 hours, _respectively . The FWHMs were 68, 68, 69 and 66 nm, respectively, and the device efficiencies were 44, 56, 52 and 48 cd/A, respectively. In this case, the heterogeneous nature provides benefits in device stability. Comparative Example 9 (with homogeneous compound 17) and device example 10 (with heterocompatible compound 18) had T _{80% for} 7 and 3 hours, _respectively . The FWHM is 74 and 71 nm, respectively, and the device efficiencies are about 23 and 27 cd/A, respectively. In this case, the heterogeneous nature provides benefits in terms of line width and device efficiency. Comparative Example 11 (with homogeneous compound 1) and device example 12 (with heterocompatible compound 2) all had T _{80% for} 4 hours. The FWHM is 76 and 74 nm, respectively, and the device efficiencies are about 35 and 44 cd/A, respectively. In this case, the heterogeneous nature provides benefits in terms of line width and device efficiency. Summary device results, based on the use of heterologous analogs as dopant emitters, often have one or more improvements in device stability, line width, or device efficiency.

Ir(6-alkyl ppy) type complexes have a particularly narrow line width. The FWHMs of device examples 6, 7, and 8 were 68, 69, and 66 nm, respectively. It is believed to be in 6 Substitutions have this effect because they contribute to the spatial effect of the Ir complex, resulting in a relatively long N-Ir bond that shifts to a narrower emission. Thus, the Ir(ppy) complex has a 6-alkyl group and is particularly useful for achieving narrow ray linewidths and improved device stability with heterogeneous properties without significantly increasing the evaporation temperature compared to the homogeneous counterpart.

As can be seen from Table 1, the host material and ETL2 materials are also important in influencing the performance and life of the device. For example, device example 6 uses compound 35 as the emitter, CBP as the host material and HTP as the ETL2, device example 7 uses compound 35 as the emitter, compound H as the host material and compound H as the ETL2, and device example 16 uses the compound 35 is used as an emitter, and compound G is used as a host material and compound H is used as ETL2. The efficiencies are 56, 52 and 56 cd/A, respectively. T _80% is 18, 85 and 210 hours at about L ₀ =15000 cd/m ² , respectively. The FWHM is 68, 69 and 70 nm, respectively. The CIEs were (0.317, 0.625), (0.316, 0.625) and (0.313, 0.625), respectively. Although the efficiency, FWHM and CIE are similar, the device having the compound H and the compound G as a host material has an improved lifetime, which is increased by about 5 and 12 times, respectively, compared to a device having CBP as a host material. Likewise, Device Example 8 used Compound 11 as an emitter, Compound H as a host material and Compound H as ETL2, and Device Example 17 used Compound 11 as an emitter, Compound G as a host material, and Compound H as ETL2. The efficiencies are 48 and 56 cd/A, respectively. T _80% was 38 hours at L ₀ = 13000 cd/m ² and 117 hours at L ₀ = 16000 cd/m ² , respectively. The FWHM is 66 and 65 nm, respectively. The CIEs were (0.298, 0.626) and (0.290, 0.630), respectively. In this case, the use of the compound G as a host material provides a slight improvement in efficiency and CIE, and the device life is improved by at least 3 times as compared with the device in which the compound H is used as a host material. Compound H based on a triphenyl compound (U.S. Application No. 61/017,506) which is a host material of a phosphorescent OLED can be superior to carbazole as a host material. Further, the compound G based on a dibenzothiophene compound (U.S. Application No. 61/017,480) which is a host material of a phosphorescent OLED can be advantageously used as a host material. It is especially advantageous to use a combination of a stretched triphenyl host material and a linked triphenyl ETL2. It is even more advantageous to use a combination of a dibenzothiophene host material and a linked triphenyl ETL2.

It may be difficult to synthesize an Irppy complex having a 6-alkyl group by direct mismatching of a ligand with Ir(acac) ₃ . For example, the synthesis of intermediate I in the preparation of compound 11 is reported in WO 2006/014599 A2. The direct mismatch of the ligand with Ir(acac) ₃ gave only 5.4% of Intermediate I. However, in the preparation of compound 11, intermediate I was synthesized by means of Ir(L) ₂ ^t Buacac. The yield of the final step was significantly better (74%). Similarly, compound 17 and compound 32 were synthesized by the Ir(L) ₂ ^t Buacac pathway in a modified yield compared to the direct mismatch method. Without wishing to be bound by theory, it is believed that the ^t Buacac ligand is a better leaving group than the acac ligand, which makes it easier to be displaced by the third ligand in the formation of the 叁Ir complex. This method provides high yield synthesis of ruthenium complexes for cyclometallated ligands having photoactive space requirements in OLEDs.

It is to be understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be replaced by other materials and structures without departing from the spirit of the invention. Thus, the invention as claimed may include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. Should The various theories as to why the invention is feasible are not intended to be limiting.

100‧‧‧Organic lighting device

110‧‧‧Substrate

115‧‧‧Anode

120‧‧‧ hole injection layer

125‧‧‧ hole transport layer

130‧‧‧Electronic barrier

135‧‧‧ emission layer

140‧‧‧ hole barrier

145‧‧‧Electronic transport layer

150‧‧‧electron injection layer

155‧‧‧Protective layer

160‧‧‧ cathode

162‧‧‧First conductive layer

164‧‧‧Second conductive layer

200‧‧‧Inverted OLED

210‧‧‧Substrate

215‧‧‧ cathode

220‧‧‧Emission layer

22 hole transmission layer

230‧‧‧Anode

Figure 1 shows an organic light emitting device.

Figure 2 shows an inverted organic light emitting device without a separate electron transport layer.

Figure 3 shows the ruthenium complex.

Figure 4 shows the reaction in the synthetic route.

(no component symbol description)

Claims (17)

a heterocyclic compound having the following formula, Wherein n = 1 or 2; R ₁ and R ₄ are independently selected from the group consisting of hydrogen, alkyl and aryl; at least one of R ₁ and R ₄ is alkyl; and R ₂ , R ₃ and R ₅ are hydrogen . The compound of claim 1, wherein the compound is selected from the group consisting of: An organic light-emitting device comprising: an anode; a cathode; and an organic emission layer disposed between the anode and the cathode, the organic layer comprising a compound having the formula: Wherein n = 1 or 2; R ₁ and R _{4 are} independently selected from the group consisting of hydrogen, alkyl and aryl; at least one of R ₁ and R ₄ is alkyl; and R ₂ , R ₃ and R ₅ are hydrogen. The device of claim 3, wherein the compound is selected from the group consisting of: The device of claim 3, wherein the organic emissive layer further comprises a host material. The device of claim 5, wherein the host material is a compound comprising a carbazole group, a co-triphenyl group or a dibenzothiophene group. The device of claim 3, wherein the compound is: The device of claim 7, wherein the organic emission layer comprises a host material and an emission dopant, and the compound 11 is the emission dopant. The device of claim 7, wherein the compound 11 emits a dopant and the compound H: The main material. The device of claim 7, wherein the compound 11 emits a dopant and the compound G: The main material. The device of claim 3, wherein the compound is: The device of claim 11, wherein the organic emissive layer comprises a host material and an emissive dopant, and the compound 35 is the emissive dopant. The device of claim 11, wherein the compound 35 emits a dopant and the compound H: The main material. The device of claim 11, wherein the compound 35 emits a dopant and the compound G: The main material. An organic light-emitting device comprising: an anode; a cathode; and an organic emission layer disposed between the anode and the cathode, the organic layer comprising a compound having the formula: Wherein n = 1 or 2; R ₁ , R ₂ , R ₅ and R _{6 are} independently selected from the group consisting of hydrogen, alkyl and aryl; at least one of R ₂ and R ₅ is alkyl; R ₄ is selected from hydrogen And a group of alkyl and aryl groups, and may represent a mono-, di- or tri-substituted; and R ₃ and R ₇ are hydrogen, wherein the organic emissive layer further comprises a host material, wherein the host material is: An organic light-emitting device comprising: an anode; a cathode; and an organic emission layer disposed between the anode and the cathode, the organic layer comprising a compound having the formula: Wherein n = 1 or 2; R ₁ , R ₂ , R ₅ and R _{6 are} independently selected from the group consisting of hydrogen, alkyl and aryl; at least one of R ₂ and R ₅ is alkyl; R ₄ is selected from hydrogen a group consisting of an alkyl group and an aryl group, and which may represent a mono-, di- or tri-substituted; and R ₃ and R ₇ are hydrogen, wherein the organic emissive layer further comprises a host material, wherein the host material is: An organic light-emitting device comprising: an anode; a cathode; and an organic emission layer disposed between the anode and the cathode, the organic layer comprising a compound having the formula: Wherein n=1 or 2; R ₁ and R _{4 are} independently selected from the group consisting of hydrogen, alkyl and aryl; at least one of R ₁ and R ₄ is alkyl; and R ₃ is selected from hydrogen, alkyl and aryl. a group of constituents, and R ₃ may represent a mono-, di- or tri-substituted; and R ₂ and R ₅ are hydrogen, wherein the organic emissive layer further comprises a host material, wherein the host material is: